Updated on 2024/05/19

写真a

 
MATANO Yoshihiro
 
Organization
Academic Assembly Institute of Science and Technology Fundamental Sciences Professor
Graduate School of Science and Technology Fundamental Sciences Professor
Faculty of Science Department of Science Professor
Title
Professor
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Degree

  • 博士(理学) ( 1994.11   京都大学 )

Research Areas

  • Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry

Research History (researchmap)

  • Niigata University   Faculty of Science Department of Science   Professor

    2017.4

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  • Niigata University   Graduate School of Science and Technology Fundamental Sciences   Professor

    2013.4

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  • Niigata University   Faculty of Science Department of Chemistry Organic and Biological Chemistry   Professor

    2013.4 - 2017.3

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  • Kyoto University   Graduate School of Engineering   Associate Professor

    2002.4 - 2013.3

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  • Kyoto University   Graduate School of Science   Research Assistant

    1995.4 - 2002.3

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  • Kyoto University   Faculty of Science   Research Assistant

    1990.11 - 1995.3

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Research History

  • Niigata University   Faculty of Science Department of Science   Professor

    2017.4

  • Niigata University   Graduate School of Science and Technology Fundamental Sciences   Professor

    2013.4

  • Niigata University   Graduate School of Science and Technology Fundamental Sciences   Professor

    2013.4

  • Niigata University   Abolition organization Organic and Biological Chemistry   Professor

    2013.4 - 2017.3

Education

  • Kyoto University   Graduate School, Division of Natural Science   化学専攻

    - 1990.10

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    Country: Japan

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  • Kyoto University   Faculty of Science   化学科

    - 1987.3

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    Country: Japan

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Professional Memberships

Studying abroad experiences

  • 米国ワシントン大学(University of Washington)   文部省在外研究員長期

    1996.9 - 1997.8

 

Papers

  • Synthesis, Structure, and Redox and Optical Properties of 5,10,15,20-Tetraaryl-5-azaporphyrinium Salts. International journal

    Yuta Kudoh, Emi Suzuki, Hikari Ochiai, Kakeru Ise, Yoshifumi Kimura, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

    Chemistry (Weinheim an der Bergstrasse, Germany)   e202302148   2023.8

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    The fundamental properties of azaporphyrins can be modulated over a wide range by changing the number of meso-nitrogen atoms. Reported herein are the first examples of 5,10,15,20-tetraaryl-5-azaporphyrinium (MTAMAP) salts, which were prepared via metal-templated cyclization of the corresponding zinc(II) and copper(II) complexes of 10-aryl-1-chloro-19-benzoyl-5,15-dimesityl-10-azabiladiene-ac. The inclusion of one meso-nitrogen atom in the 5,10,15,20-tetraarylporphyrin skeleton considerably changes the redox and optical properties as well as the degree of aromaticity of the porphyrin ring. The present findings suggest that MTAMAP salts would be promising scaffolds for the development of new azaporphyrin-based ionic fluorophores and photosensitizers.

    DOI: 10.1002/chem.202302148

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  • 9‐(Diphenylphosphoryl)‐10‐(phenylethynyl)anthracene Derivatives: Synthesis and Implications for the Substituent and Solvent Effects on the Light‐Emitting Properties Reviewed

    Nina Murayama, Joel Hao Jorolan, Mao Minoura, Haruyuki Nakano, Tadaaki Ikoma, Yoshihiro Matano

    ChemPhotoChem   6 ( 9 )   e202200100   2022.9

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    Authorship:Last author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    DOI: 10.1002/cptc.202200100

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    Other Link: https://onlinelibrary.wiley.com/doi/full-xml/10.1002/cptc.202200100

  • Synthesis, Electrochemical Behavior, and Catalytic Activity of Cobalt Complexes of 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids Reviewed

    Yuna Satoh, Yuta Kudoh, Ko Furukawa, Yoshihiro Matano

    Organic Letters   24 ( 21 )   3839 - 3843   2022.6

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    DOI: 10.1021/acs.orglett.2c01411

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  • Synthesis, Optical Properties, and Electrochemical Behavior of 5,10,15,20-Tetraaryl-5,15-diazaporphyrin-Amine Hybrids Reviewed

    Yuna Satoh, Yutaro Fujita, Naoya Muramatsu, Ko Furukawa, Tadaaki Ikoma, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

    ChemPlusChem   86 ( 10 )   1476 - 1486   2021.10

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    This work reports a series of covalently linked hybrids comprising 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (M-TADAP; M = Ni, Zn, Cu) and amines. M-TADAP-amine hybrids were prepared via the metal-templated cyclization of the corresponding metal(II)-dipyrrin complexes and redox reactions on the DAP unit. In the UV/vis/near-IR absorption spectra of the hybrids containing an 18 pi-electron DAP ring, broad charge-transfer bands were observed, reflecting the electron-donating property of the para-aminophenyl groups and the electron-accepting property of the 18 pi TADAP dication. The electrochemical behavior of the M-TADAP-amine hybrids was strongly dependent on the structure of the peripheral amine units. Further electrochemical oxidation of the hybrids bearing N-Ph groups conceivably generated amine-centered radicals, which sequentially underwent irreversible coupling to form benzidine-linked M-TADAP polymer films. The Ni-TADAP-benzidine polymer exhibited the electric conductivity of 2x10(-3) S m(-1).

    DOI: 10.1002/cplu.202100429

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  • Doubly Strapped Redox-Switchable 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids: Promising Platforms for the Evaluation of Paratropic and Diatropic Ring-Current Effects Reviewed

    Hikari Ochiai, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano

    The Journal of Organic Chemistry   86 ( 3 )   2283 - 2296   2021.2

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    This paper presents a novel series of chemically stable and redox-switchable 20π, 19π, and 18π5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (TADAPs) that have two alkyl-chain straps above and below the diazaporphyrin ring. Three types of doubly strapped TADAPs were prepared as nickel(II) complexes using meso-N-(2,6-dihydroxyphenyl)-substituted TADAP and the corresponding aliphatic diacids as precursors. Theoretical calculations revealed that regardless of their oxidation states, all strapped TADAPs had essentially flat π-planes. It was found that the alkyl-chain straps slightly affected the optical and electrochemical properties of the DAP rings, particularly in the oxidized forms. 1H NMR spectroscopy was used to evaluate the antiaromatic character of the 20πTADAPs and the aromatic character of the 18πTADAP dications, and it was observed that they displayed paratropic and diatropic ring-current effects, respectively, on the chemical shifts of methylene protons in the spatially separated alkyl chains. The degree of shielding and deshielding depended on the position of the methylene units; it decreased with increase in separation from the π-plane and central axis of the porphyrin ring. The NMR experiments also revealed that the degree of the diatropic ring currents was clearly related to the π-electron density of the porphyrin ring; the ring-current effects decreased as the charge increased from 0 to +2. These findings are also qualitatively supported by the nucleus-independent chemical shifts.

    DOI: 10.1021/acs.joc.0c02433

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  • Effects of the Peripheral Substituents, Central Metal, and Solvent on the Photochemical and Photophysical Properties of 5,15-Diazaporphyrins Reviewed

    Satoshi Omomo, Ryosuke Fukuda, Tomoaki Miura, Tatsuya Murakami, Tadaaki Ikoma, Yoshihiro Matano

    ChemPlusChem   84 ( 6 )   740 - 745   2019

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    DOI: 10.1002/cplu.201900087

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    Other Link: https://onlinelibrary.wiley.com/doi/full-xml/10.1002/cplu.201900087

  • Direct and Regioselective Amination of β-Unsubstituted 5,15-Diazaporphyrins with Amines: A Convenient Route to Near-Infrared-Responsive Diazaporphyrin Sensitizers Reviewed

    Satoshi Omomo, Takuma Sugai, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

    Angewandte Chemie - International Edition   57 ( 14 )   3797 - 3800   2018.3

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    We have established a convenient method for the base-promoted direct amination of β-unsubstituted 5,15-diazaporphyrins (DAPs) with secondary and primary amines to produce 3,7,13,17-tetraamino- and 3-amino-DAPs, respectively, regioselectively. The amino groups attached at the periphery cause significant red shifts of the absorption bands as a result of their perturbation of the HOMO and/or LUMO in the DAP π-system. The palladium complex of a 3,7,13,17-tetrakis(diphenylamino)-DAP generated singlet oxygen in high yield under irradiation with near-infrared light.

    DOI: 10.1002/anie.201800471

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  • Syntheses, Properties, and Catalytic Activities of Metal(II) Complexes and Free Bases of Redox-Switchable 20 pi, 19 pi, and 18 pi 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids Reviewed

    Keisuke Sudoh, Takaharu Satoh, Toru Amaya, Ko Furukawa, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

    CHEMISTRY-A EUROPEAN JOURNAL   23 ( 64 )   16364 - 16373   2017.11

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    In spite of significant advances in redox-active porphyrin-based materials and catalysts, little attention has been paid to 20 pi and 19 pi porphyrins because of their instability in air. Here we report the meso-modification of 5,10,15,20-tetraarylporphyrin with two nitrogen atoms, which led to redox-switchable 20 pi, 19 pi, and 18 pi 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (TADAPs). Three kinds of metal(II) complexes and free bases of TADAP were prepared by the metal-templated annulation of the corresponding metal-bis(dipyrrin) complexes. The inductive and resonance effects of the meso-nitrogen atoms on the aromatic, optical, electrochemical, and magnetic properties of the entire TADAP pi-systems were assessed by using various spectroscopic measurements and density functional theory calculations. The aromaticity and pi-pi* electronic transition energies of the TADAPs varied considerably, and were shown to be dependent on the oxidation states of the pi-systems. In contrast to the isoelectronic 5,10,15,20-tetraarylporphyrin derivatives, the 20 pi and 19 pi TADAPs were chemically stable under air. In particular, the 19 pi TADAP radical cations were extremely stable towards dioxygen, moisture, and silica gel. This reflected the low-lying singly occupied molecular orbitals of their pi-systems and the efficient delocalization of their unshared electron spin. The capability of MgTADAP to catalyze aerobic biaryl formation from aryl Grignard reagents was demonstrated, which presumably involved a 19 pi/20 pi redox cycle.

    DOI: 10.1002/chem.201703664

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  • Redox-Switchable 20-, 19-, and 18-Electron 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoid Nickel(II) Complexes Reviewed

    Takaharu Satoh, Mao Minoura, Haruyuki Nakano, Ko Furukawa, Yoshihiro Matano

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   55 ( 6 )   2235 - 2238   2016.2

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    The first examples of air-stable 20-electron 5,10,15,20-tetraaryl-5,15-diaza-5,15-dihydroporphyrins, their 18-electron dications, and the 19-electron radical cation were prepared through metal-templated annulation of nickel(II) bis(5-arylamino-3-chloro-8-mesityldipyrrin) complexes followed by oxidation. The neutral 20-electron derivatives are antiaromatic and the cationic 18-electron derivatives are aromatic in terms of the magnetic criterion of aromaticity. The meso Natoms in these diazaporphyrinoids give rise to characteristic redox and optical properties for the compounds that are not typical of isoelectronic 5,10,15,20-tetraarylporphyrins.

    DOI: 10.1002/anie.201510734

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  • Synthesis and Structure-Property Relationships of Phosphole-Based pi Systems and Their Applications in Organic Solar Cells Reviewed

    Yoshihiro Matano

    CHEMICAL RECORD   15 ( 3 )   636 - 650   2015.6

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    Phosphole is a chemically tunable heterole, and its pi-conjugated derivatives are potential candidates for optoelectronic materials. This account describes recent developments in the synthesis and structure-property relationships of pi-conjugated phosphole derivatives made by my research group. Thiophene-phosphole-styrene, phosphole-acetylene-arene, oligophosphole, polyphosphole, areno[c]phosphole, and phosphole-heterole pi systems are synthesized using titanacycle-mediated metathesis and palladium-catalyzed cross-coupling reactions. The structural, optical, and electrochemical properties of selected compounds are discussed. Initial results on some applications of thiophene-phosphole copolymers, acenaphtho[c]phospholes, and amin-terthiophene-phosphole donor-pi-acceptor dyes in organic solar cells are described. These results give valuable information and guidelines for designing new phosphorus-containing organic materials for molecular electronics.

    DOI: 10.1002/tcr.201402101

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  • Synthesis of Chain Type and Fused π-Conjugated Phosphole Derivatives

    MATANO Yoshihiro, IMAHORI Hiroshi

    Journal of Synthetic Organic Chemistry, Japan   70 ( 6 )   629 - 639   2012.1

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    Phosphole has a low aromaticity and exhibits characteristic optical and electrochemical properties derived from the phosphorus-bridged 1,3-diene π system. In addition, phosphole has an active lone pair at phosphorus. The most remarkable feature of the phosphole-based π-systems is that their fundamental properties are tunable by chemical functionalizations at the phosphorus center. In this regard, phosphole-based π-systems are now regarded as one of the future materials for use in optoelectronics. In this article, we would like to briefly summarize our recent results on the synthesis of novel π-conjugated phosphole derivatives with representative examples, which contain phosphole-vinylene, phosphole-acetylene, phosphole-heterole, phosphole-benzene, phosphole-phosphole, benzo[c]phosphole, acenaphtho[c]phoshole, and diacenaphtho[b,d]phosphole skeletons. The target compounds were successfully prepared by two main approaches, titanacycle method and Stille coupling. Selected structural, optical, and electrochemical data for a few derivatives are also presented. The results described herein would give valuable information and guidelines for designing phosphole-based opto-electrochemical materials.

    DOI: 10.5059/yukigoseikyokaishi.70.629

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  • Theoretical study on counter anion- and solvent-dependent fluorescence quenching mechanism of 2-phenylbenzo[b]phospholium salts

    Sara Suzuki, Kosuke Imamura, Kaori Fujii, Yoshifumi Kimura, Yoshihiro Matano, Masahiro Higashi, Hirofumi Sato

    Journal of Molecular Liquids   382   2023.7

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    Recently reported highly fluorescent 2-phenylbenzo[b]phospholium salt shows an interesting photochemical property. While the counter anion and solvent dependency indicate that the salt is mainly responsible for the absorption and fluorescence spectra, the fluorescence decay clearly depends on the counter anion. In the present study, the detailed mechanism is elucidated using quantum chemical computation and its hybrid with statistical mechanics called 3D-RISM-SCF. Based on the careful exploration of plausible structures of the ion pairs in the methanol and dichloromethane solution, we identify the structure of the charge transfer state, the key on the photoprocess.

    DOI: 10.1016/j.molliq.2023.121934

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  • Substituent Effect on the Excited-State Dynamics of Benzo[<i>b</i>]phospholium Salts Investigated Using Picosecond Time-Resolved Spectroscopy

    Kaori Fujii, Atsuro Matsumoto, Takayuki Oka, Yuta Kudoh, Hiroaki Nakagomi, Yoshihiro Matano, Yoshifumi Kimura

    Bulletin of the Chemical Society of Japan   96 ( 7 )   686 - 692   2023.7

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    DOI: 10.1246/bcsj.20230071

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  • Synthesis and optical properties of 3,5-bis(10-phenylanthracen-9-yl)benzene-appended porphyrins

    Akane Umemiya, Haruyuki Nakano, Nanami Iwaya, Tadaaki Ikoma, Yoshihiro Matano

    Journal of Porphyrins and Phthalocyanines   A - L   2023.6

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    <jats:p> Singlet–singlet and triplet-triplet energy-transfer processes between anthracenes and porphyrins have received considerable attention in materials chemistry. Herein, we report the first examples of 3,5-bis(10-phenylanthracen-9-yl)benzene-appended porphyrins (BPABPs) designed to study intramolecular energy transfer between two chromophores. The Curtius rearrangement of 3,5-bis(10-phenylanthracen-9-yl)benzoyl azide in the presence of the platinum(II) complex of 5,10,15-tris(3,5-di-tert-butylphenyl)-20-(3-hydroxyphenyl)porphyrin or its free base in toluene afforded the corresponding BPABP. Spectroscopy, cyclic voltammetry, and density functional theory calculations revealed that the anthracene and porphyrin [Formula: see text]-electron systems of the BPABPs are not conjugated and consequently do not affect each other’s absorption properties. In contrast, the BPABPs exhibited considerably different luminescence properties to those of phenyl 3,5-bis(10-phenylanthracen-9-yl)carbamate and 5,10,15-tris(3,5-di-tert-butylphenyl)-20-(3-methoxyphenyl)porphyrins; the anthracene units of the BPABPs show considerably quenched fluorescence compared to that of the reference anthracene, indicative of efficient intramolecular singlet–singlet energy transfer from the anthracene to the porphyrin unit. The phosphorescence quantum yield of the Pt complex of BPABP is comparable to that of the reference Pt-porphyrin, which suggests that intramolecular triplet-triplet energy transfer from the Pt-porphyrin to the anthracene unit is inefficient. The present findings improve our understanding of how structural factors and excited-state energy levels affect energy transfer and triplet-triplet annihilation upconversion processes of covalently linked bisanthracene-appended porphyrins. </jats:p>

    DOI: 10.1142/s1088424623500840

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  • Synthesis and Optical Properties of 1,2,5,10-Tetraphenylanthra[2,3-b]phosphole Derivatives. Reviewed International journal

    Yuta Kudoh, Kaori Fujii, Yoshifumi Kimura, Mao Minoura, Yoshihiro Matano

    The Journal of Organic Chemistry   87 ( 15 )   10493 - 10500   2022.8

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    1,2,5,10-Tetraphenylanthra[2,3-b]phosphole oxides and 1-methyl-1,2,5,10-tetraphenylanthra[2,3-b]phospholium salts were prepared, and their optical properties were investigated. The substituent at the para position and the fused anthracene moiety were found to exert significant impacts on the fluorescence properties of the P-bridged 2-styrylanthracene skeleton.

    DOI: 10.1021/acs.joc.2c01107

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  • Copper(II) Complexes of 10,20-Diaryl-5,15-diazaporphyrin: Alternative Synthesis, Excited State Dynamics, and Substituent Effect on the <sup>1</sup>O<inf>2</inf>-Generation Efficiency Reviewed

    Hikari Ochiai, Tomoaki Miura, Tadaaki Ikoma, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

    Bulletin of the Chemical Society of Japan   95 ( 3 )   427 - 432   2022

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    The synthesis, excited state dynamics, and substituent effect on the 1O2-generation efficiency of several copper(II) complexes of 5,15-diazaporphyrin (CuDAPs) bearing peripheral substituents are reported. 10,20-Diaryl-CuDAPs were prepared via a new method consisting of metal-templated cyclization and N-dealkylation as key steps. The effect of the β-substituents on the optical and redox properties of CuDAP was stronger than that of the meso-aryl groups, which can be explained by considering the characteristics of the HOMO and LUMO of the DAP ring. The excited state dynamics and 1O2-generation efficiency of CuDAPs were studied using time-resolved spectroscopic techniques; the electronic effect of the meso-aryl groups on the triplet lifetime and 1O2-generation quantum yield was relatively weak, whereas that of the β-(1-pyrazolyl) groups was appreciable. The analysis of the temperature dependence of phosphorescence spectra of 10,20-bis(2,4,6-trimethylphenyl)-CuDAP allowed the energy gap between the excited trip-quartet and trip-doublet states to be determined. The relatively long triplet lifetimes of CuDAPs show their potential for future application as photosensitizers.

    DOI: 10.1246/bcsj.20220002

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  • Synthesis of Hydrophilic Copper(II) Complexes of 5,10,15,20-Tetraaryl-5,15-diazaporphyrins Substituted with Carboxy or (2,3-Dihydroxypropyl)carbamoyl Groups Invited Reviewed

    Yuki Shimizu, Yoshihiro Matano

    Journal of Porphyrins and Phthalocyanines   25   1005 - 1014   2021.8

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    Porphyrins containing hydrophilic auxiliaries have received considerable attention. Herein we report the first examples of strongly hydrophilic copper(II) complexes of 5,10,15,20-tetraaryl-5,15-diazaporphyrins (TADAPs) substituted with carboxy or (2,3-dihydroxypropyl)carbamoyl groups. Metal-templated cyclization reactions of a common dipyrrin precursor with nickel(II) or copper(II) acetate afforded the corresponding metal(II) complexes of 5,10,15,20-tetrakis(4-alkoxycarbonylphenyl)-5,15-diazaporphyrin (M-TADAP-COOR; M = Ni, Cu) as air-stable 19[Formula: see text] radical cations, which were reversibly interconvertible with 20[Formula: see text]- and 18[Formula: see text]-electron states by redox reactions. NMR spectroscopy of 20[Formula: see text] and 18[Formula: see text] Ni-TADAP-COORs revealed antiaromatic and aromatic characteristics, respectively. Alkaline hydrolysis of the 19[Formula: see text] Cu-TADAP-COOR afforded a carboxylic acid, Cu-TADAP-COOH, which was freely soluble in water under basic conditions, but poorly soluble under neutral or acidic conditions. Dehydrative condensation of Cu-TADAP-COOH with 2,3-bis((tert-butyldimethylsilyl)oxy)propan-1-amine followed by deprotection of the silyl groups afforded an amide, Cu-TADAP-CONHR, with four (2,3-dihydroxypropyl)carbamoyl groups. Although the 20[Formula: see text] Cu-TADAP-CONHR was poorly soluble in water, oxidation of its DAP ring notably changed the solubility, and the resulting 18[Formula: see text] dication was homogeneously dispersed in neutral water. Cyclic voltammetry of the present TADAP derivatives showed the 21[Formula: see text]/20[Formula: see text], 20[Formula: see text]/19[Formula: see text] and 19[Formula: see text]/18[Formula: see text] redox couples in the range of −1.8 to +0.2 V vs. Fc/Fc[Formula: see text]. Furthermore, Cu-TADAP-CONHR exhibited reversible redox processes in neutral water. This study shows that TADAP could be a potential platform for the development of hydrophilic DAP-based materials.

    DOI: 10.1142/s1088424621500917

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  • π-Conjugated Molecules Containing Tetrathiafulvalene and Benzo[b]phosphole Oxide: Synthesis, Structure, and Electrochemical and Optical Properties Reviewed

    Shunki Ikeda, Aya Yoshimura, Takashi Shirahata, Yoshihiro Matano, Yohji Misaki

    Chemistry Letters   50 ( 8 )   1581 - 1585   2021.8

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    DOI: 10.1246/cl.210218

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  • Excited-State Intramolecular Proton Transfer Reaction and Ground-State Hole Dynamics of 4′-N,N-Dialkylamino-3-hydroxyflavone in Ionic Liquids Studied by Transient Absorption Spectroscopy Reviewed

    Hanamichi Miyabayashi, Kaori Fujii, Takumi Watanabe, Yoshihiro Matano, Takatsugu Endo, Yoshifumi Kimura

    The Journal of Physical Chemistry B   125 ( 20 )   5373 - 5386   2021.5

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    DOI: 10.1021/acs.jpcb.1c02360

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  • Synthesis and optical, magnetic, and electrochemical properties of 5,10,15,20-tetraaryl-5,15-diazaporphyrin — tertiary amine conjugates Invited Reviewed

    Keisuke Sudoh, Yuna Satoh, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano

    Journal of Porphyrins and Phthalocyanines   24 ( 01n03 )   286 - 297   2020.1

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    We report on the synthesis and optical, magnetic, and electrochemical properties of nickel(II) and copper(II) complexes of 5,10,15,20-tetraaryl-5,15-diazaporphyrin–tertiary amine (TADAP–TA) conjugates. Metal-templated cyclization reactions of 9-(4-(dimethylamino)phenyl)amino-1-chloro-5-mesityldipyrrin and 9-(4-(diphenylamino)phenyl)amino-1-chloro-5-mesityldipyrrin (mesityl = 2,4,6-trimethylphenyl) with nickel(II) or copper(II) acetate afforded the corresponding metal(II) complexes of TADAP–TA. The 20[Formula: see text], 19[Formula: see text], and 18[Formula: see text] oxidation states of the DAP ring in the TADAP – TAs were reversibly interconvertible by redox reactions. NMR spectroscopy of the 20[Formula: see text] and 18[Formula: see text] Ni-TADAP – TAs revealed their antiaromatic and aromatic characters, respectively, whereas electron paramagnetic resonance spectroscopy of the 19[Formula: see text] Ni-TADAP–TAs showed effective delocalization of an unshared electron spin in the DAP ring. The interconversion between the three oxidation states of TADAP – TAs also caused a distinct change in the optical properties of the DAP [Formula: see text]-electron system. Notably, all the 18[Formula: see text] dications exhibited weak and broad absorption bands in the near infrared region owing to the charge-transfer from the peripheral tertiary amine units (donor) to the cationic DAP center (acceptor). Cyclic voltammetry of TADAP – TAs exhibited the reversible 20[Formula: see text]/19[Formula: see text] and 19[Formula: see text]/18[Formula: see text] redox couples and the irreversible amine oxidation at the periphery. The electrochemical oxidation of the Ni-TADAP–triphenylamine conjugate generated reactive ammoniumyl radicals, which underwent intermolecular coupling to form a polymer of TADAP–TA on the electrode surface.

    DOI: 10.1142/s1088424619500822

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  • Synthesis of Redox-switchable 5,15-Dialkyl-10,20-diaryl-5,15-diazaporphyrins and Diversification of their N-Alkyl Groups Reviewed

    Mai Mutoh, Keisuke Sudoh, Ko Furukawa, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

    Asian Journal of Organic Chemistry   8 ( 3 )   352 - 355   2019.3

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    Nickel(II) and copper(II) complexes of redox-switchable 20 pi, 19 pi, and 18 pi 5,15-dialkyl-10,20-diaryl-5,15-diazaporphyrins were prepared through a metal-templated cyclization method. Furthermore, the terminal silyloxy groups in the peripheral N-alkyl chains were transformed into hydroxy groups by deprotection. It is worth noting that redox reactions between the 19 pi and 18 pi systems bearing hydroxy groups caused a change in the water solubility of the diazaporphyrin chromophore.

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  • Synthesis and Properties of Redox-Switchable Zinc Complexes of 10,15,20-Triaryl-15-aza-5-oxaporphyrin Reviewed

    Keisuke Sudoh, Ko Furukawa, Haruyuki Nakano, Soji Shimizu, Yoshihiro Matano

    Heteroatom Chemistry   29 ( 5-6 )   e21456   2018.12

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    The synthesis, aromaticity, and optical and electrochemical properties of zinc(II) complexes of 10,15,20-triaryl-15-aza-5-oxaporphyrin (TriAAOP) were investigated. Metal-templated cyclization of a zinc(II) 1,19-dichloro-5,10,15-triaryl-10-azatetrapyrrin complex with an oxygen source afforded 20 pi TriAAOP in the neutral form. Oxidation of 20 pi TriAAOP with silver (I) hexafluorophosphate generated the 19 pi radical cation or 18 pi dication depending on the content of oxidant used. The interconversion between the three oxidation states (18 pi, 19 pi, and 20 pi) resulted in distinct changes in the aromaticity and optical properties of the 15-aza-5-oxaporphyrin pi-system. Nuclear magnetic resonance spectroscopy of 20 pi TriAAOP revealed its antiaromatic character, whereas that of the 18 pi TriAAOP dication showed its aromatic character. The combined effect of the two meso-heteroatoms was directly reflected in the redox properties of the porphyrin ring; TriAAOP was reduced more easily and more difficult to oxidize than the zinc(II) complex of 5,10,15,20-tetraaryl-5,15-diaz-aporphyrin (TADAP). In the ultraviolet-visible-near-infrared spectra of the materials, the lowest-energy electronic excitations of the 19 pi and 18 pi TriAAOP derivatives were considerably red-shifted compared with those of the isoelectronic TADAP derivatives. Based on the results of density functional theory calculations, it was concluded that the observed differences between TriAAOP and TADAP would arise from the high electronegativity of oxygen; specific frontier orbitals of the TriAAOP pi-systems were energetically stabilized relative to those of the TADAP pi-system. The present findings corroborate that the meso-modification of a porphyrin rings with different kinds of heteroatoms is a promising strategy to fine tune their light-response properties that are switchable by reversible single electron transfer processes.

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  • Synthesis of 3,5-Disubstituted BODIPYs Bearing N-Containing Five-Membered Heteroaryl Groups via Nucleophilic C-N Bond Formation Reviewed

    Takaharu Satoh, Kaori Fujii, Yoshifumi Kimura, Yoshihiro Matano

    Journal of Organic Chemistry   83 ( 9 )   5274 - 5281   2018.5

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    Aromatic substitution reactions were applied to the divergent synthesis of a series of symmetrically and unsymmetrically 3,5-disubstituted BODIPYs bearing N-heteroaryl groups. Furthermore, the effect of N-heteroaryl substituents at the 3- and 5-positions on the optical and photophysical properties of the BODIPY π-electron system was elucidated.

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  • Phosphole-Thiophene Hybrid: A Dual Role of Dithieno[3,4- b:3′,4′- d] phosphole as Electron Acceptor and Electron Donor Reviewed

    Tomohiro Higashino, Keiichi Ishida, Takaharu Satoh, Yoshihiro Matano, Hiroshi Imahori

    Journal of Organic Chemistry   83 ( 6 )   3397 - 3402   2018.3

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    We have synthesized dithieno[3,4-b:3′,4′-d]phosphole derivatives as a new type of thiophene-fused phospholes. These dithienophospholes were found to show intramolecular charge transfer interactions by introducing electron-donating or -withdrawing groups on the peripheral aryl groups. Namely, they exhibit the unique hybrid character of electron-withdrawing phosphole and electron-donating thiophene.

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  • Phosphole-Thiophene Hybrid: A Dual Role of Dithieno[3,4-b:3 ',4 '-d]phosphole as Electron Acceptor and Electron Donor Reviewed

    Tomohiro Higashino, Keiichi Ishida, Takaharu Satoh, Yoshihiro Matano, Hiroshi Imahori

    JOURNAL OF ORGANIC CHEMISTRY   83 ( 6 )   3397 - 3402   2018.3

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  • Direct and Regioselective Amination of β-Unsubstituted 5,15-Diazaporphyrins with Amines: A Convenient Route to Near-Infrared-Responsive Diazaporphyrin Sensitizers Reviewed International journal

    Satoshi Omomo, Takuma Sugai, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

    Angewandte Chemie   130 ( 14 )   3859 - 3800   2018.3

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    We have established a convenient method for the base-promoted direct amination of β-unsubstituted 5,15-diazaporphyrins (DAPs) with secondary and primary amines to produce 3,7,13,17-tetraamino- and 3-amino-DAPs, respectively, regioselectively. The amino groups attached at the periphery cause significant red shifts of the absorption bands as a result of their perturbation of the HOMO and/or LUMO in the DAP π-system. The palladium complex of a 3,7,13,17-tetrakis(diphenylamino)-DAP generated singlet oxygen in high yield under irradiation with near-infrared light.

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  • β-functionalization of 5, 15-diazaporphyrins with phosphorus, oxygen, and sulfur-containing substituents Reviewed

    Takuma Sugai, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

    Bulletin of the Chemical Society of Japan   91 ( 8 )   1264 - 1266   2018

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    The β-functionalization of 5, 15-diazaporphyrins (DAPs) with phosphoryl, phenoxy, sulfanyl, and sulfonyl groups was achieved by either cross-coupling or aromatic nucleophilic substitution reactions of β-bromo- and β, β′-dibromo-DAPs. The heteroatom-containing functional groups at the β- positions strongly affected the redox properties of the DAP π-systems.

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  • Redox Switchable 19π and 18π 5,10,20-Triaryl-5,15-diazaporphyrinoid–Nickel(II) Complexes Reviewed

    Keisuke Sudoh, Takuroh Hatakeyama, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano

    Journal of Porphyrins and Phthalocyanines   22 ( 7 )   542 - 551   2018

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    The synthesis and optical, electrochemical, and magnetic properties of nickel(II) complexes of 5,10,20-triaryl-5,15-diazaporphyrin (TriADAP) are reported. Metal-templated cyclization of unsymmetrically substituted nickel(II)-bis(1-amino-9-chloro-5-mesityldipyrrin; mesityl = 2,4,6-trimethylphenyl) complexes afforded the corresponding TriADAPs or 5-aryl-15-benzyl-10,20-dimesityl-5,15-diazaporphyrin, depending on the combination of base and solvent. The latter macrocycle was converted to TriADAP by deprotection of the N-benzyl group through Pd/C-promoted hydrogenation. TriADAPs were isolated in both 18 pi (cation) and 19 pi (neutral) forms. The interconversion between these two oxidation states resulted in a distinct change in the optical properties of the DAP pi-system. NMR spectroscopy of the 18 pi TriADAP cations showed that they had aromatic character, whereas EPR spectroscopy of the 19 pi TriADAP showed a highly delocalized electron spin of the pi-radical. The para substituents of the N-aryl groups of TriADAPs had a small but distinct impact on their HOMO and LUMO energies. The change in the net charge of one electron was directly reflected in the redox properties of the DAP ring; TriADAP was more easily reduced and less easily oxidized than DAP. The difference in the net charge was also reflected by the shielding of the pyrrolic beta-protons observed in the H-1 NMR spectra. The present results confirm that TriADAP is a highly promising framework for constructing a new class of azaporphyrin-based materials with 18 pi-19 pi redox-switchable optical and magnetic properties.

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  • Regioselective functionalization at the 7-position of 1,2,3-triphenylbenzo[b] phosphole oxide via P=O-directed lithiation Reviewed

    Ayana Wakatsuki, Mariko Yukimoto, Mao Minoura, Kaori Fujii, Yoshifumi Kimura, Yoshihiro Matano

    Dalton Transactions   47 ( 21 )   7123 - 7127   2018

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    Various 7-substituted benzo[b]phosphole derivatives were prepared by PO-directed lithiation of 1,2,3-triphenylbenzo[b]phosphole P-oxide and subsequent iodination and cross-coupling reactions. The electron-donating groups introduced at the 7-position produced dramatic solvatofluorochromism owing to the strong charge-transfer character of the excited state of the entire π-system.

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  • Segregated Donor-Acceptor Columns in Liquid Crystals That Exhibit Highly Efficient Ambipolar Charge Transport (vol 133, pg 10736, 2011) Reviewed

    Hironobu Hayashi, Wataru Nihashi, Tomokazu Umeyama, Yoshihiro Matano, Shu Seki, Yo Shimizu, Hiroshi Imahori

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   139 ( 39 )   13957 - 13957   2017.10

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  • Effects of counter anions, P-substituents, and solvents on optical and photophysical properties of 2-phenylbenzo[b]phospholium salts Reviewed

    Yoshinari Koyanagi, Shogo Kawaguchi, Kaori Fujii, Yoshifumi Kimura, Takahiro Sasamori, Norihiro Tokitoh, Yoshihiro Matano

    DALTON TRANSACTIONS   46 ( 29 )   9517 - 9527   2017.8

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    In this work, we investigated the effects of counter anions, P-substituents, and solvents on the optical and photophysical properties of 2-phenylbenzo[b]phospholium salts in solution. A series of 2-phenylbenzo[b] phospholium salts was prepared by P-alkylation or P-phenylation of 1,2-diphenylbenzo[b]phosphole followed by anion exchange reactions. X-ray crystallographic analyses of six benzo[b] phospholium salts showed that each phosphorus center has an onium nature with an essentially tetrahedral geometry. H-1 NMR and steady-state UV-vis absorption and fluorescence spectroscopic measurements of these phospholium salts revealed the pivotal role of counter-anion solvation. The observed results are discussed on the basis of the association-dissociation equilibrium between a contact ion pair (CIP) and a solvent-separated ion pair (SSIP) in solution. The hexafluorophosphates exist as SSIPs and emit intense fluorescence, irrespective of the P-substituents and solvents. In contrast, the iodides are present as SSIPs in methanol but exist as equilibrium mixtures of the two emitting species, SSIP and CIP, in dichloromethane. As a consequence, fluorescence intensities of the iodides varied significantly depending on the solvents, P-substituents, and solution concentrations. These findings were studied in more detail using time-resolved fluorescence spectroscopy and fluorescence titration measurements. The light-emitting properties of the 2-phenylbenzo[b] phospholium halides in the CIPs rely on heavy atom effects derived from the counter halide anions on the S-1 state of the adjacent cationic benzo[b] phosphole pi-systems. The present study suggests that 2-arylbenzo[b] phospholium salts would be promising scaffolds for developing new phosphole-based ionic fluorophores that are capable of responding to external stimuli such as anionic species and solvents.

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  • Correction to: Segregated donor-acceptor columns in liquid crystals that exhibit highly efficient ambipolar charge transport (Journal of the American Chemical Society (2011) 133 (10736-10739) DOI: 10.1021/ja203822q) Reviewed

    Hironobu Hayashi, Wataru Nihashi, Tomokazu Umeyama, Yoshihiro Matano, Shu Seki, Yo Shimizu, Hiroshi Imahori

    Journal of the American Chemical Society   133 ( 28 )   10736 - 10739   2017.7

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    Liquid crystalline donor (i.e., phthalocyanine) was covalently linked to acceptor (i.e, fullerene) to achieve efficient charge-transport properties in a liquid crystalline phase. The columnar structure exhibited highly efficient ambipolar charge-transport character, demonstrating the potential utility of the strategy in organic electronics. © 2011 American Chemical Society.

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  • Excited-State Proton Transfer of Cyanonaphthols in Protic Ionic Liquids: Appearance of a New Fluorescent Species Reviewed

    Kaori Fujii, Yoshiro Yasaka, Masakatsu Ueno, Yoshinari Koyanagi, Sora Kasuga, Yoshihiro Matano, Yoshifumi Kimura

    Journal of Physical Chemistry B   121 ( 24 )   6042 - 6049   2017.6

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    Excited-state proton transfer (ESPT) of 5-cyano-2-naphthol (5CN2) and 5,8-dicyano-2-naphthol (DCN2) in three different protic ionic liquids (PILs), triethylammonium trifluoromethanesulfonate ([N222H][CF3SO3]), triethylammonium methanesulfonate ([N222H][CH3SO3]), and triethylammonium trifluoroacetate ([N222H][CF3COO]), was studied by time-resolved fluorescence. In [N222H][CF3SO3], both 5CN2 and DCN2 showed fluorescence only from ROH∗ (normal form of substituted naphthol in the excited states), indicating that no ESPT occurred in [N222H][CF3SO3]. For 5CN2 in [N222H][CH3SO3], fluorescence bands from ROH∗ and RO-∗ (anionic form of substituted naphthol in the excited states) were observed, indicating that 5CN2 could dissociate proton to surrounding solvents and form RO-∗. More interestingly, 5CN2 in [N222H][CF3COO] and DCN2 in [N222H][CH3SO3] and [N222H][CF3COO] showed an anomalous fluorescence band around 470 nm (5CN2) or around 520 nm (DCN2) which has not been reported previously. The kinetics of each fluorescent component of 5CN2 and DCN2 was analyzed on the basis of the time profile of fluorescence intensity. Plausible ESPT schemes of 5CN2 and DCN2 were discussed on the basis of the kinetics and the basicity of anion in PILs. (Graph Presented).

    DOI: 10.1021/acs.jpcb.7b03658

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  • Unsymmetrically Substituted Donor--Acceptor-Type 5,15-Diazaporphyrin Sensitizers: Synthesis, Optical and Photovoltaic Properties Reviewed

    Satoshi Omomo, Yukihiro Tsuji, Kenichi Sugiura, Tomohiro Higashino, Haruyuki Nakano, Hiroshi Imahori, Yoshihiro Matano

    CHEMPLUSCHEM   82 ( 5 )   695 - 704   2017.5

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    The first examples of unsymmetrical -substituted donor--acceptor (D--A)-type 5,15-diazaporphyrin (DAP) sensitizers with both p-aminophenyl and p-carboxyphenyl groups at their peripheral 3-, 7-, 13-, and/or 17-positions have been synthesized for use in dye-sensitized solar cells (DSSCs). UV/Vis absorption and emission spectroscopy, electrochemical measurements, and DFT calculations revealed that these D--A dyes exhibit high light-harvesting properties over the whole visible range because of the intrinsic charge-transfer character of their electronic transitions. The cell performances of TiO2-based DSSCs fabricated with the newly prepared DAP derivatives were evaluated under standard AM1.5 conditions. Among the four dyes examined, 13,17-bis(p-carboxyphenyl)-3,7-bis[p-(N,N-dimethylamino)phenyl]-DAP showed the highest power conversion efficiency (2.0%), which was 20times larger than that obtained with 3-(p-carboxyphenyl)-DAP. These results show that the DAP chromophore could be used as the electron-accepting unit in various types of functional dyes.

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  • Nitrogen-Bridged Metallodiazaporphyrin Dimers: Synergistic Effects of Nitrogen Bridges and meso-Nitrogen Atoms on Structure and Properties Reviewed

    Masahiro Kawamata, Takuma Sugai, Mao Minoura, Yasuhisa Maruyama, Ko Furukawa, Cole Holstrom, Victor N. Nemykin, Haruyuki Nakano, Yoshihiro Matano

    CHEMISTRY-AN ASIAN JOURNAL   12 ( 7 )   816 - 821   2017.4

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    NH-bridged and pyrazine-fused metallodiazaporphyrin dimers have been prepared from nickel(II) and copper(II) complexes of 3-amino-5,15-diazaporphyrin by Pd-catalyzed C-N cross-coupling and oxidative dimerization reactions, respectively. The synergistic effects of the nitrogen bridges and meso-nitrogen atoms play major roles in enhancing the light-harvesting properties and delocalization of an electron spin over the entire pi-skeletons of the metallodiazaporphyrin dimers.

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  • Synthesis of Dibenzophosphole Oxides from Dibenzothiophene Dioxides and Phenylphosphine by Two Successive SNAr Reactions Reviewed

    Mitsuki Onoda, Yoshinari Koyanagi, Hayate Saito, M. Bhanuchandra, Yoshihiro Matano, Hideki Yorimitsu

    ASIAN JOURNAL OF ORGANIC CHEMISTRY   6 ( 3 )   257 - 261   2017.3

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    One-pot treatment of dibenzothiophene dioxides with phenylphosphine and KOH in DMSO at ambient temperature provides the corresponding dibenzophosphole oxides after oxidative workup. Substitution of the endocyclic SO2 unit with PPh could proceed via an intermolecular SNAr reaction of the dioxides with potassium phenylphosphide followed by another SNAr reaction in an intramolecular fashion. Various dibenzophospholes have been synthesized from readily available dibenzothiophene dioxides and were investigated from a photophysical viewpoint.

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  • Synthesis of Aza-, Oxa-, and Thiaporphyrins and Related Compounds Invited Reviewed

    Yoshihiro Matano

    Chemical Reviews   117 ( 4 )   3138 - 3191   2017.2

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    Chemical modification at the periphery with nitrogen or chalcogens is a highly promising strategy to diversify the optical, electrochemical, magnetic, and coordination properties of the porphyrin family. Indeed, various kinds of phthalocyanines and related benzo-annelated azaporphyrinoids have been synthesized, and their fundamental properties have been extensively investigated. However, the synthesis of heteroatom-containing porphyrins in which the peripheral methine groups are partially replaced with nitrogen or chalcogens remains a considerable challenge. In this review, we will focus mainly on recent advances in the synthesis of aza-, oxa-, and thiaorphyrins and related compounds, including historically important examples.

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  • Ring-Strain Effects in Base-Induced Sommelet-Hauser Rearrangement: Application to Successive Stereocontrolled Transformations Reviewed

    Eiji Tayama, Kazutoshi Watanabe, Yoshihiro Matano

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY   ( 21 )   3631 - 3641   2016.7

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    The base-induced Sommelet-Hauser (S-H) rearrangement of azetidine-2-carboxylic acid ester-derived ammonium salts into 2-aryl-substituted derivatives was demonstrated. The ring-strain of four-membered N-heterocycles enables efficient generation of the desired ylide intermediate and enhances the rate of the S-H rearrangement. The asymmetric version of the rearrangement was characterized by excellent levels of successive chirality transmissions. The regio- and stereo-controlled nucleophilic ring opening of the rearrangement products produced quaternary -aryl amino acid esters with excellent enantiopurities.

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  • Effects of boryl, phosphino, and phosphonio substituents on optical, electrochemical, and photophysical properties of 2,5-dithienylphospholes and 2-phenyl-5-thienylphospholes Reviewed

    Yoshinari Koyanagi, Yoshifumi Kimura, Yoshihiro Matano

    Dalton Transactions   45 ( 5 )   2190 - 2200   2016.1

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    © 2016 The Royal Society of Chemistry. The optical, electrochemical, and photophysical properties of Mes2B- (Mes = 2,4,6-trimethylphenyl), Ph2P-, or Ph2MeP+-substituted 2,5-dithienylphospholes and 2-phenyl-5-thienylphospholes are reported. The Mes2B- and Ph2P-substituted derivatives were prepared via regioselective lithiation and metathesis at the thiophene rings of the corresponding unsubstituted π-systems. The Ph2MeP+-substituted derivatives (phosphonium salts) were obtained via methylation of the Ph2P-substituted π-systems. The optical and electrochemical data and density functional theory calculations showed that the highest occupied molecular orbital and lowest unoccupied molecular orbital energies of these α,α′-linked thiophene-phosphole π-systems were sensitive to the intrinsic nature of the B and P substituents. The fluorescence quantum yields (Φf) of the Ph2MeP+-substituted derivatives varied considerably depending on the counter anion, concentration, and solvent, but the π-π∗ transition energies were unchanged. The emitting ability of the Ph2MeP+-substituted 2,5-dithienylphosphole π-system changed significantly from Φf= 0.07 to 0.87. These findings were investigated using time-resolved fluorescence spectroscopy and fluorescence titration measurements. The results show that phosphonium iodides were present in the equilibrium mixtures of three or two emitting ion pairs in CH2Cl2. The light-emitting abilities of the Ph2MeP+-substituted derivatives rely on heavy atom effects derived from the counter halide anions.

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  • Synthesis and Photophysical Properties of Two Diazaporphyrin-Porphyrin Hetero Dimers in Polar and Nonpolar Solutions Reviewed

    Fawzi Abou-Chahine, Daisuke Fujii, Hiroshi Imahori, Haruyuki Nakano, Nikolai V. Tkachenko, Yoshihiro Matano, Helge Lemmetyinen

    Journal of Physical Chemistry B   119 ( 24 )   7328 - 7337   2015.6

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    Two diazaporphyrin (DAP)-porphyrin hetero dimers, in β-meso and β-β configurations, were prepared to study their photoinduced intramolecular electron transfer properties. The two meso nitrogen atoms in the porphyrin ring of DAP change its redox potential, making DAP more easily reduced, compared to its porphyrin counterpart. A charge-transfer from porphyrin to DAP in both hetero dimers was verified by versatile optical spectroscopic methods. The steady-state fluorescence spectra indicated an efficient intramolecular exciplex formation for both dimers. For the β-meso dimer, ultrafast time-resolved spectroscopic methods revealed the subpicosecond formation of two types of primary short-living (1-18 ps) intramolecular exciplexes, which relaxed in toluene to form a long-living final exciplex (1.4 ns) followed by a longer-living charge transfer complex (&gt
    5 ns). However, in benzonitrile, the lifetime of the final exciplex was longer (660 ps) as was that of the charge transfer complex (180 ps). The β-β analogue formed similar short-living exciplexes in both solvents, but the final exciplex and the charge transfer state had significantly shorter lifetimes. The electrochemical redox potential measurements and density functional theory calculations supported the proposed mechanism.

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  • Comparison of 2-arylnaphtho[2,3- b ]phospholes and 2-arylbenzo[ b ]phospholes: Effects of 2-Aryl groups and fused arene moieties on their optical and photophysical properties Reviewed

    Yoshihiro Matano, Yuta Motegi, Shinsuke Kawatsu, Yoshifumi Kimura

    Journal of Organic Chemistry   80 ( 11 )   5944 - 5950   2015.6

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    © 2015 American Chemical Society. Suzuki-Miyaura cross-coupling reactions were used in the divergent synthesis of a series of 2-arylnaphtho[2,3-b]phosphole P-oxides and their benzo[b]phosphole counterparts. We elucidated the electronic and steric effects of the 2-aryl groups and fused arene moieties on the optical and photophysical properties of these two types of phosphole-based π-systems.

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  • Comparison of electronic effects of beta-aryl substituents on optical and electrochemical properties of 5,15-diazaporphyrin pi-systems Reviewed

    Satoshi Omomo, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano

    JOURNAL OF PORPHYRINS AND PHTHALOCYANINES   19 ( 6 )   775 - 785   2015.6

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    The syntheses and optical/electrochemical properties of 3-aryl-10,20-dimesityl-5,15-diazaporphyrin-metal complexes (MDAPs; mesityl = 2,4,6-trimethylphenyl; M = Ni, Zn) are reported. Treatment of 3-bromo-MDAPs with arylboronic acids in the presence of a Pd catalyst and a bulky phosphine ligand in a dioxane-water mixed solvent afforded the corresponding 3-aryl-MDAPs in moderate to good yields. X-ray crystallographic analysis of p-EtO2CC6H4-NiDAP showed that the beta-aryl group was tilted toward the NiDAP ring, with a dihedral angle of 21.7 degrees. In the UV-visible absorption spectra, all the Ar-MDAPs showed intense Q-bands attributable to HOMO-to-LUMO transitions. The para substituents were found to influence the HOMO energies, which eventually resulted in fine tuning of the HOMO-LUMO gaps of the diazaporphyrin chromophores. It is worth noting that the p-Ph2NC6H4-ZnDAP showed broad absorption and emission bands in the visible-near-infrared regions. The large Stokes shifts and their linear solvation energy relationships vs. orientation polarizability show that this Ph2N-substituted derivative has intrinsically high charge transfer from the triphenylamine (donor) to the ZnDAP (acceptor) unit. These experimental observations were supported by theoretical calculations for model Ar-ZnDAP compounds. These results confirm that the introduction of a highly electron-donating aryl group at the peripheral beta-carbon is a promising strategy for enhancing the light-harvesting and light-emitting abilities of diazaporphyrin-based pi-systems in the visible-near-infrared regions.

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  • Optical, electrochemical, and magnetic properties of pyrrole- And thiophene-bridged 5,15-diazaporphyrin dimers Reviewed

    Satoshi Omomo, Yasuhisa Maruyama, Ko Furukawa, Taniyuki Furuyama, Haruyuki Nakano, Nagao Kobayashi, Yoshihiro Matano

    Chemistry - A European Journal   21 ( 5 )   2003 - 2010   2015.1

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    The first examples of pyrrole- and thiophenebridged 5,15-diazaporphyrin (DAP) dimers are prepared through Stille coupling reactions of nickel(II) and copper(II) complexes of 3-bromo-10,20-dimesityl-5,15-diazaporphyrin (mesityl = 2,4,6-trimethylphenyl) with the respective 2,5-bis-(tributylstannyl)heteroles. The effects of the heterole spacers and meso nitrogen atoms on the optical, electrochemical, and magnetic properties of the DAP dimers are investigated by UV/Vis absorption spectroscopy, density functional theory calculations, magnetic circular dichroism spectroscopy, cyclic voltammetry, and EPR spectroscopy. The heterole spacers are found to have a significant impact on the electronic transitions over the entire p-system. In particular, the pyrrolebridged DAP dimers exhibit high light-harvesting potential in the low-energy visible/near-infrared region owing to the intrinsic charge-transfer character of the lowest excitation.

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  • N,S,P-hybrid donor-π-acceptor organic dyes for dye-sensitized solar cell: Synthesis, optical properties, and photovoltaic performances Invited Reviewed

    Yoshihiro Matano, Yukiko Hayashi, Haruyuki Nakano, Hiroshi Imahori

    Heteroatom Chemistry   25 ( 6 )   533 - 547   2014.6

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    New donor-π-acceptor organic (D-π-A) dyes composed of triarylamine, oligothiophene, and phosphole subunits were prepared, and their optical and photovoltaic properties were investigated. The regioselective α-lithiation of the thiophene ring of 2-(thiophen-2-yl)phospholes bearing an ester group, followed by treatment with tributyltin chloride afforded 2-(5-(tributylstannyl)thiophen-2-yl)phosphole derivatives, which underwent Stille coupling with 5′-(p-(diarylamino)phenyl)-5-bromo-2,2′-bithiophene to give triarylamine-terthiophene-phosphole hybrid π systems bearing the terminal ester group. The alkaline hydrolysis of the ester group yielded the target dyes, bearing the carboxylic acid anchoring group. The UV-vis absorption spectra of the new N,S,P-hybrid dyes displayed broad and intense π-π∗ transitions with two absorptionmaxima in the visible region. Density functional theory (DFT) calculations of two dye models revealed that each highest occupied molecular orbital (HOMO) resides on the triarylamine-oligothiophene π network, whereas each lowest unoccupied molecular orbital (LUMO) is basically located on the phosphole subunit. In addition, the time-dependent DFT calculations of the models showed that the lowest energy bands of these hybrid dyes are mainly consisted of the HOMO-to-LUMO+1 and HOMO-to-LUMO transitions with the large intramolecular charge-transfer character. The N,S,P-hybrid-dye-sensitized TiO2 cells exhibitedmoderate power conversion efficiencies of up to 5.6%. The present findings corroborate the potential utility of the phosphole skeletons as the acceptor components in the D-π-A sensitizers.

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  • Phosphole- and Benzodithiophene- Based Copolymers: Synthesis and Application in Organic Photovoltaics Reviewed

    Yoshihiro Matano, Hiroshi Ohkubo, Tetsushi Miyata, Yusuke Watanabe, Yukiko Hayashi, Tomokazu Umeyama, Hiroshi Imahori

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY   2014 ( 10 )   1620 - 1624   2014.4

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    Two kinds of phosphole- and benzodithiophene-based copolymers bearing PV=O or PV=NSO2C8H17 functions were prepared by Pd-CuI-promoted Stille coupling reactions, and their optical and electrochemical properties were investigated. Bulk heterojunction organic photovoltaic devices comprised of the new P,S-bridged copolymers and (6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) exhibited power conversion efficiencies of up to 0.65-% under AM1.5 irradiation at 100 mW-cm-2. Copyright © 2014 WILEY-VCH Verlag GmbH &amp
    Co. KGaA, Weinheim.

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  • Covalently Linked 5,15-Diazaporphyrin Dimers: Promising Scaffolds for a Highly Conjugated Azaporphyrin pi System Reviewed

    Yoshihiro Matano, Daisuke Fujii, Tarou Shibano, Ko Furukawa, Tomohiro Higashino, Haruyuki Nakano, Hiroshi Imahori

    CHEMISTRY-A EUROPEAN JOURNAL   20 ( 12 )   3342 - 3349   2014.3

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    The first examples of - directly linked, acetylene-bridged, and butadiyne-bridged 5,15-diazaporphyrin dimers have been prepared by palladium-catalyzed coupling reactions of nickel(II) and copper(II) complexes of 3-bromo-10,20-dimesityl-5,15-diazaporphyrin (mesityl=2,4,6-trimethylphenyl). The effects of the linking modes and meso-nitrogen atoms on the structural, optical, electrochemical, and magnetic properties of the distributed systems were investigated by using X-ray crystallography, UV/Vis absorption spectroscopy, DFT calculations, cyclic voltammetry, and ESR spectroscopy. Both the electronic and steric effects of the meso-nitrogen atoms play an important role in the highly coplanar geometry of the directly linked dimers. The direct - linkage produces enhanced conjugation and electron-spin coupling between the two diazaporphyrin units.

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  • Slow charge recombination and enhanced photoelectrochemical properties of diazaporphyrin-fullerene linked dyad Reviewed

    M. Yamamoto, Y. Takano, Y. Matano, K. Stranius, N.V. Tkachenko, H. Lemmetyinen, H. Imahori

    Journal of Physical Chemistry C   118 ( 4 )   1808 - 1820   2014

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    Diazaporphyrin-C-60 linked dyad has been prepared to assess intrinsic electron transfer properties of diazaporphyrins for the first time. The dyad exhibited the efficient formation of a charge-separated state which has a lifetime 4x longer than that of the corresponding porphyrin-C-60 linked dyad with the same spacer. In accordance with this elongation, a SnO2 nanostructured electrode modified with the diazaporphyrin-C-60 dyad also revealed enhanced photocurrent generation in the visible region in comparison with that with the porphyrin-C-60 dyad. These results show that diazaporphyrins are highly promising building blocks for the construction of artificial photosynthesis and solar energy conversion.

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  • Synthesis of 2-Alkenyl- and 2-Alkynyl-benzo[b]phospholes by Using Palladium-Catalyzed Cross-Coupling Reactions Reviewed

    Yoshihiro Matano, Yukiko Hayashi, Kayo Suda, Yoshifumi Kimura, Hiroshi Imahori

    ORGANIC LETTERS   15 ( 17 )   4458 - 4461   2013.9

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    Heck, Stille, and Sonogashira reactions of 2-bromobenzo[b]phosphole P-oxide afforded a series of 2-alkenyl- and 2-alkynyl-benzo[b]phosphole P-oxides. The charge-transfer character of the new benzo[b]phosphole pi-systems in the excited state is enhanced by the terminal electron-donating substituents. Furthermore, the C-Sn cross-coupling of the bromide was applied to the facile synthesis of a new Stille-coupling precursor, 2-stannylbenzo[b]phosphole.

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  • Synthesis and Photovoltaic Properties of Phenylethynyl-substituted Diazaporphyrin Reviewed

    Kei Kurotobi, Kyosuke Kawamoto, Yuuki Toude, Yamato Fujimori, Yuriko Kinjo, Seigo Ito, Yoshihiro Matano, Hiroshi Imahori

    CHEMISTRY LETTERS   42 ( 7 )   725 - 726   2013.7

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    Carboxyphenylethynyl-substituted diazaporphyrin has been synthesized to assess the utility of diazaporphyrins in dye-sensitized solar cells for the first time. The diazaporphyrin-sensitized TiO<sub>2</sub> cell exhibited photocurrent generation in the visible region of 400–700 nm together with a power conversion efficiency of 0.08%.

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  • Synthesis and Charge-Carrier Transport Properties of Poly(phosphole P-alkanesulfonylimide)s Reviewed

    Yoshihiro Matano, Hiroshi Ohkubo, Yoshihito Honsho, Arihiro Saito, Shu Seki, Hiroshi Imahori

    ORGANIC LETTERS   15 ( 4 )   932 - 935   2013.2

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    A new class of polyphospholes bearing alkanesulfonylimino moieties on the phosphorus(V) centers was prepared by the Pd-Cul-promoted Stille coupling reaction to investigate the charge-carrier transport properties of the pi-networks of polyphospholes. Time-of-flight measurements have revealed that the poly(phosphole P-imide)s possess ambipolar charge-carrier mobilities of up to mu(electron) = 6 x 10(-3) cm(2) V-1 s(-1) and mu(hole) = 4 x 10(-3) cm(2) V-1 s(-1).

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  • Synthesis and Structure-Property Relationships of 2,2 '-Bis(benzo[b]phosphole) and 2,2 '-Benzo[b]phosphole-Benzo[b]heterole Hybrid pi Systems Reviewed

    Yukiko Hayashi, Yoshihiro Matano, Kayo Suda, Yoshifumi Kimura, Yoshihide Nakao, Hiroshi Imahori

    CHEMISTRY-A EUROPEAN JOURNAL   18 ( 50 )   15972 - 15983   2012.12

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    The first comprehensive study of the synthesis and structureproperty relationships of 2,2'-bis(benzo[b]phosphole)s and 2,2'-benzo[b]phospholebenzo[b]heterole hybrid p systems is reported. 2-Bromobenzo[b]phosphole P-oxide underwent copper-assisted homocoupling (Ullmann coupling) and palladium-catalyzed cross-coupling (Stille coupling) to give new classes of benzo[b]phosphole derivatives. The benzo[b]phospholebenzo[b]thiophene and -indole derivatives were further converted to P,X-bridged terphenylenes (X=S, N) by a palladium-catalyzed oxidative cycloaddition reaction with 4-octyne through the C beta H activation. X-ray analyses of three compounds showed that the benzo[b]phosphole-benzo[b]heterole derivatives have coplanar p planes as a result of the effective conjugation through inter-ring C?C bonds. The pp* transition energies and redox potentials of the cis and trans isomers of bis(benzo[b]phosphole) P-oxide are very close to each other, suggesting that their optical and electrochemical properties are little affected by the relative stereochemistry at the two phosphorus atoms. The optical properties of the benzo[b]phospholebenzo[b]heterole hybrids are highly dependent on the benzo[b]heterole subunits. Steady-state UV/Vis absorption/fluorescence spectroscopy, fluorescence lifetime measurements, and theoretical calculations of the non-fused and acetylene-fused benzo[b]phospholebenzo[b]heterole p systems revealed that their emissive excited states consist of two different conformers in rapid equilibrium.

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  • Free Base and Metal Complexes of 5,15-Diaza-10,20-dimesitylporphyrins: Synthesis, Structures, Optical and Electrochemical Properties, and Aromaticities Reviewed

    Yoshihiro Matano, Tarou Shibano, Haruyuki Nakano, Yoshifumi Kimura, Hiroshi Imahori

    INORGANIC CHEMISTRY   51 ( 23 )   12879 - 12890   2012.12

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    The synthesis, structures, optical and electrochemical properties, and aromaticity of a series of 5,15-diaza-10,20-dimesitylporphyrins (M-DAP; M = Pb, H-2, Ni, Pd, Pt, Zn; mesityl = 2,4,6-trimethylphenyl) are reported. Treatment of mesityl-substituted bis(5,5'-dibromodipyrrin) with sodium azide in the presence of lead(II) acetylacetonate afforded Pb-DAP, which was quantitatively converted to H-2-DAP by acidolysis. The free base H-2-DAP reacted with palladium(II), platinum(II), and zinc(II) salts to give Pd-DAP, Pt-DAP, and Zn-DAP, respectively. The crystal structures, optical and electrochemical properties, and aromaticities of these beta-unsubstituted M-DAPs were comprehensively investigated by X-ray crystallography, UV-vis absorption/fluorescence spectroscopy, nanosecond flash photolysis, cyclic and differential pulse voltammetry, NMR spectroscopy, and density functional theory calculations. The obtained data show that replacement of the 5- and 15-methine carbons with nitrogen atoms alters the intrinsic properties of the porphyrin 18 pi system as follows: (i) the coordination spheres at the N-4 core become contracted while keeping high planarity; (ii) the Q bands are red shifted and largely intensified; (iii) the electron-accepting ability is enhanced, whereas the electron-donating ability is reduced; (iv) the radiative decay rates from the S-1 state are enhanced; and (v) the aromaticity of the 18 pi circuit is slightly reduced in terms of both geometric and magnetic criteria. These optical and electrochemical properties of M-DAPs stem from their characteristic frontier orbitals; two HOMOs and two LUMOs are nondegenerate as a result of the incorporation of the electronegative nitrogen atoms at the two meso positions. In addition, the group 10 metals incorporated at the core finely tune the fundamental properties of DAP pi systems through inductive effects as well as d pi-p pi antibonding orbital interactions; the HOMO-LUMO gaps of the group 10 metal complexes increase in the order Ni-DAP &lt; Pd-DAP &lt; Pt-DAP.

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  • alpha,alpha '-Diarylacenaphtho[1,2-c]phosphole P-Oxides: Divergent Synthesis and Application to Cathode Buffer Layers in Organic Photovoltaics Reviewed

    Yoshihiro Matano, Arihiro Saito, Yuto Suzuki, Tooru Miyajima, Seiji Akiyama, Saika Otsubo, Emi Nakamoto, Shinji Aramaki, Hiroshi Imahori

    CHEMISTRY-AN ASIAN JOURNAL   7 ( 10 )   2305 - 2312   2012.10

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    A divergent method for the synthesis of a,a'-diarylacenaphtho[1,2-c]phosphole P-oxides has been established; a,a-dibromoacenaphtho[c]phosphole P-oxide, which was prepared through a TiII-mediated cyclization of 1,8-bis(trimethylsilylethynyl)naphthalene, underwent a Stille coupling with three different kinds of aryltributylstannanes to afford the a,a'-diarylacenaphtho[c]phosphole P-oxides in moderate to good yields. X-ray crystallographic analyses and UV/Vis absorption/fluorescence measurements have revealed that the degree of p-conjugation, the packing motif, the electron-accepting ability, and the thermal stability of the acenaphtho[c]phosphole p-systems are finely tunable with the a-aryl substituents. All the P?O and P?S derivatives exhibited high stability in their electrochemically reduced state. To use this class of arene-fused phosphole p-systems as n-type semiconducting materials, we evaluated device performances of the bulk heterojunction organic photovoltaics (OPV) that consist of poly(3-hexylthiophene), an indene-C70 bisadduct, and a cathode buffer layer. The insertion of the diarylacenaphtho[c]phosphole P-oxides as the buffer layer was found to improve the power conversion efficiency of the polymer-based OPV devices.

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  • Synthesis of Chain Type and Fused pi-Conjugated Phosphole Derivatives Invited Reviewed

    Yoshihiro Matano, Hiroshi Imahori

    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN   70 ( 6 )   629 - 639   2012.6

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    Phosphole has a low aromaticity and exhibits characteristic optical and electrochemical properties derived from the phosphorus-bridged 1,3-diene π system. In addition, phosphole has an active lone pair at phosphorus. The most remarkable feature of the phosphole-based π-systems is that their fundamental properties are tunable by chemical functionalizations at the phosphorus center. In this regard, phosphole-based π-systems are now regarded as one of the future materials for use in optoelectronics. In this article, we would like to briefly summarize our recent results on the synthesis of novel π-conjugated phosphole derivatives with representative examples, which contain phosphole-vinylene, phosphole-acetylene, phosphole-heterole, phosphole-benzene, phosphole-phosphole, benzo[c]phosphole, acenaphtho[c]phoshole, and diacenaphtho[b,d]phosphole skeletons. The target compounds were successfully prepared by two main approaches, titanacycle method and Stille coupling. Selected structural, optical, and electrochemical data for a few derivatives are also presented. The results described herein would give valuable information and guidelines for designing phosphole-based opto-electrochemical materials.

    DOI: 10.5059/yukigoseikyokaishi.70.629

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  • Nickel(II) and Copper(II) Complexes of beta-Unsubstituted 5,15-Diazaporphyrins and Pyridazine-Fused Diazacorrinoids: Metal-Template Syntheses and Peripheral Functionalizations Reviewed

    Yoshihiro Matano, Tarou Shibano, Haruyuki Nakano, Hiroshi Imahori

    CHEMISTRY-A EUROPEAN JOURNAL   18 ( 20 )   6208 - 6216   2012.5

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    The present paper reports the first comprehensive study on the synthesis, structures, optical and electrochemical properties, and peripheral functionalizations of nickel(II) and copper(II) complexes of beta-unsubstituted 5,15-diazaporphyrins (M-DAP; M=Ni, Cu) and pyridazine-fused diazacorrinoids (Ni-DACX; X=N, O). These two classes of compounds were constructed starting from mesityldipyrromethane by a metaltemplate method. Ni-DAP and Cu-DAP were prepared in high yields by the reaction of the respective metalbis(dibromodipyrrin) complexes with NaN3CuX (X=I, Br), whereas Ni-DACN and Ni-DACO were formed as predominant products by the reaction with NaN3. In both cases, the metal centers change their geometry from tetrahedral to square planar during the aza-annulation; X-ray crystallographic analyses of M-DAPs showed highly planar diazaporphyrin p planes. The Q band of Ni-DAP was redshifted and intensified compared with that of a nickelporphyrin reference, due to the involvement of electronegative nitrogen atoms at the meso positions. It was found that the peripheral bromination of Ni-DAP and Ni-DACO occurred regioselectively to afford Ni-DAP-Br4 and Ni-DACO-Br, respectively. These brominated derivatives underwent Stille reactions with tributyl(phenyl)stannane to give the corresponding phenylated derivatives, Ni-DAP-Ph4 and Ni-DACO-Ph. On the basis of the absorption spectra and X-ray analysis, it has been concluded that the attached phenyl groups efficiently conjugate with the diazaporphyrin p system. The present results unambiguously corroborate that the beta-unsubstituted DAPs and DACXs are promising platforms for the development of a new class of p-conjugated azaporphyrin-based materials.

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  • Preparation and Photophysical and Photoelectrochemical Properties of a Covalently Fixed Porphyrin-Chemically Converted Graphene Composite Reviewed

    Tomokazu Umeyama, Junya Mihara, Noriyasu Tezuka, Yoshihiro Matano, Kati Stranius, Vladimir Chukharev, Nikolai V. Tkachenko, Helge Lemmetyinen, Kei Noda, Kazumi Matsushige, Tetsuya Shishido, Zheng Liu, Kaori Hirose-Takai, Kazu Suenaga, Hiroshi Imahori

    CHEMISTRY-A EUROPEAN JOURNAL   18 ( 14 )   4250 - 4257   2012.4

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  • Effects of Carbon-Metal-Carbon Linkages on the Optical, Photophysical, and Electrochemical Properties of Phosphametallacycle-Linked Coplanar Porphyrin Dimers Reviewed

    Yoshihiro Matano, Kazuaki Matsumoto, Hironobu Hayashi, Yoshihide Nakao, Tatu Kumpulainen, Vladimir Chukharev, Nikolai V. Tkachenko, Helge Lemmetyinen, Soji Shimizu, Nagao Kobayashi, Daisuke Sakamaki, Akihiro Ito, Kazuyoshi Tanaka, Hiroshi Imahori

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   134 ( 3 )   1825 - 1839   2012.1

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    5-(Diphenylphosphanyl)-10,15,20-triarylporphyrins (meso-phosphanylporphyrins) underwent complex. ations with palladium(II) and platinum(II) salts to afford phosphapalladacycle- and phosphaplatinacycle-fused coplanar porphyrin dimers, respectively, via regioselective peripheral beta-C-H activation of the meso-phosphanylporphyrin ligands. The optical and electrochemical properties of these metal-linked porphyrin dimers as well as their porphyrin monomer/dimer references were investigated by means of steady-state UV-vis absorption/fluorescence spectroscopy, cyclic and differential pulse voltammetry, time-resolved spectroscopy (fluorescence and transient absorption lifetimes and spectra), and magnetic circular dichroism spectroscopy. All the observed data clearly show that the palladium(II) and platinum(II) linkers play crucial roles in the electronic communication between two porphyrin chromophores at the one-electron oxidized state and in the singlet-triplet intersystem-crossing process at the excited state. It has also been revealed that the C-Pt-C linkage makes more significant impacts on these fundamental properties than the C-Pd-C linkage. Furthermore, density functional theory calculations on the metal-linked porphyrin dimers have suggested that the antibonding d pi-p pi orbital interaction between the peripherally attached metal and adjacent pyrrolic beta-carbon atoms destabilizes the highest occupied molecular orbitals of the porphyrin pi-systems and accounts for the observed unique absorption properties. On the basis of these experimental and theoretical results, it can be concluded that the linear carbon-metal-carbon linkages weakly but definitely perturb the optical, photophysical, and electrochemical properties of the phosphametallacycle-linked coplanar porphyrin dimers.

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  • Thermal Conversion of Precursor Polymer to Low Bandgap Conjugated Polymer Containing Isothianaphthene Dimer Subunits Reviewed

    Tomokazu Umeyama, Kohei Hirose, Kei Noda, Kazumi Matsushige, Tetsuya Shishido, Hironobu Hayashi, Yoshihiro Matano, Noboru Ono, Hiroshi Imahori

    JOURNAL OF PHYSICAL CHEMISTRY C   116 ( 1 )   1256 - 1264   2012.1

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  • Pentavalent Organobismuth Reagents in Organic Synthesis: Alkylation, Alcohol Oxidation and Cationic Photopolymerization Invited

    Yoshihiro Matano

    BISMUTH-MEDIATED ORGANIC REACTIONS   311   19 - 44   2012

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    Organic transformations using organobismuth(V) reagents developed by my group are reviewed. The characteristic properties of bismuth, such as the inert pair effect, small bond dissociation energy, and polarized bonding are strongly related to the reactivity of pentavalent organobismuth compounds. The Bi(V) reagents discussed in this chapter include tetraorganylbismuthonium salts ([Ar3RBi+][X-]), triarylbismuth ylides (Ar3Bi=CHCOR), triarylbismuth imides (Ar3Bi=NCOR), triarylbismuth oxides (Ar3Bi=O), and triarylbismuth dichlorides (Ar3BiCl2). These organobismuth(V) compounds are readily accessible in a few steps from triarylbismuthanes (Ar3Bi). New and efficient carbon-carbon bond forming reactions, carbon-heteroatom bond forming reactions, alcohol oxidation, and photoinduced cationic polymerization have been investigated using these reagents. In all these reactions, the good leaving ability as well as the high nucleofugality of the triarylbismuthonio group plays a crucial role in bond-forming and bond-breaking steps.

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  • Porphyrin-appended phosphapalladacycle precatalysts: effects of central metals on the catalytic activity in a high-temperature Heck reaction Reviewed

    Yoshihiro Matano, Kazuaki Matsumoto, Tarou Shibano, Hiroshi Imahori

    JOURNAL OF PORPHYRINS AND PHTHALOCYANINES   15 ( 11-12 )   1172 - 1182   2011.11

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    The synthesis and the catalytic activity of bis(mu-chloro)-bridged, phosphapalladacyclefused diporphyrins (M-porphyrin-appended phosphapalladacycles: M = Zn, Ni, free-base), as well as the coordinating ability of their precursors, meso-phosphanylporphyrins are reported. Treatment of meso-phosphanylporphyrinatozinc(II) with an equimolar amount of PdCl(2)(NCPh)(2) caused regioselective beta-C-H activation of the porphyrin ring to produce bis(mu-chloro)-bridged Zn-porphyrin-appended phosphapalladacycle, which was further converted to the free-base-and Ni-porphyrin-appended analogs. The UV-vis absorption spectra of these palladium complexes showed weak exciton coupling between two porphyrin chromophores connected by the mu-chloro bridges. The M-porphyrinappended phosphapalladacycles behaved as precatalysts for a high temperature Heck reaction between p-bromobenzaldehyde and butyl acrylate. In a range of the catalyst-loading of 0.05-0.005 mol.%, the catalytic activity was found to significantly depend on the central metal incorporated at the porphyrin core. The Ni-porphyrin-appended phosphapalladacycle showed considerably higher turnover frequency than did the Zn-porphyrin-and free-base-porphyrin-appended counterparts. This trend in the catalytic activity does not simply correlate with the sigma-donating ability of the phosphorus center and the electron-donating ability of the porphyrin pi-systems. Instead, it is related to the durability of the precatalysts under the reaction conditions employed. The observed results corroborate that the central metal of the meso-phosphanylporphyrin ligands plays a crucial role in the active Pd(0) catalyst-loading from the porphyrin-appended phosphapalladacycles at constant efficiency.

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  • Divergent Synthesis of 2,5-Diarylphospholes Based on Cross-coupling Reactions: Substituent Effects on the Optical and Redox Properties of Benzene-Phosphole-Benzene pi-Systems Reviewed

    Yoshihiro Matano, Yusuke Kon, Arihiro Saito, Yoshifumi Kimura, Toshihiro Murafuji, Hiroshi Imahori

    CHEMISTRY LETTERS   40 ( 9 )   919 - 921   2011.9

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    Divergent synthesis of 2,5-diarylphosphole derivatives was achieved by using two kinds of Pd-catalyzed cross-coupling reactions. In addition, para- and P-substituent effects on the optical and redox properties of the benzene-phosphole-benzene pi-systems were disclosed experimentally.

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  • Optical, Electrochemical, and Photovoltaic Effects of an Electron-Withdrawing Tetrafluorophenylene Bridge in a Push-Pull Porphyrin Sensitizer Used for Dye-Sensitized Solar Cells Reviewed

    Simon Mathew, Hiroaki Iijima, Yuuki Toude, Tomokazu Umeyama, Yoshihiro Matano, Seigo Ito, Nikolai V. Tkachenko, Helge Lemmetyinen, Hiroshi Imahori

    JOURNAL OF PHYSICAL CHEMISTRY C   115 ( 29 )   14415 - 14424   2011.7

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    We have prepared a novel push-pull porphyrin with an electron-donating diarylamino group at the meso-position and an electron-withdrawing 4-carboxy-2,3,5,6-tetrafluorophenylethynyl anchoring group at the opposite meso-position to address the substitution effects of the electron-withdrawing fluorine atoms on photovoltaic properties for the first time. The fluoro-substituted porphyrin showed slightly improved light-harvesting properties when compared to the reference porphyrin in solution, due to the enhancement of charge-trapsfer character. The fluoro-substituted porphyrin-sensitized TiO2 cell exhibited a moderate power conversion efficiency of 4.6% but was lower than the corresponding Value (6.9%) of the reference porphyrin-sensitized TiO2 cell. The carboxylic group in the reference porphyrin binds to the TiO2 surface with bidentate coordination, leading to formation of the densely packed monolayer on the TiO2 surface, whereas both of the electron-withdrawing fluorine atoms and the carboxylic group of the fluoro-substituted porphyrin interact with the TiO2 surface, adopting relatively parallel orientation to the TiO2 surface with monodentate binding of the carboxylic acid to the TiO2, eventually yielding to the small surface coverage and low cell performance due to the fast charge recombination and small amount of the long-lived porphyrin radical cation. Such fundamental information may be useful for the molecular design of highly efficient dye-sensitized solar cells based on push-pull porphyrins.

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  • Segregated Donor-Acceptor Columns in Liquid Crystals That Exhibit Highly Efficient Ambipolar Charge Transport Reviewed

    Hironobu Hayashi, Wataru Nihashi, Tomokazu Umeyama, Yoshihiro Matano, Shu Seki, Yo Shimizu, Hiroshi Imahori

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   133 ( 28 )   10736 - 10739   2011.7

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    DOI: 10.1021/ja203822q

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  • Density Functional Theory Studies on Chemical Functionalization of Single-Walled Carbon Nanotubes by Bingel Reaction Reviewed

    Tomokazu Umeyama, Hiroyuki Fueno, Eisuke Kawabata, Yoshikazu Kobayashi, Kazuyoshi Tanaka, Noriyasu Tezuka, Yoshihiro Matano, Hiroshi Imahori

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   84 ( 7 )   748 - 753   2011.7

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    DOI: 10.1246/bcsj.20100326

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  • Bisquinoxaline-Fused Porphyrins for Dye-Sensitized Solar Cells Reviewed

    Hiroshi Imahori, Hiroaki Iijima, Hironobu Hayashi, Yuuki Toude, Tomokazu Umeyama, Yoshihiro Matano, Seigo Ito

    CHEMSUSCHEM   4 ( 6 )   797 - 805   2011.6

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    5,10,15,20-Tetrakis(2,4,6-trimethylphenyl)-6'-carboxylquinoxalino[2,3-b]quinoxalino[12,13-b']porphyrinatozinc(II) (ZnPBQ) is synthesized to evaluate the effects of p elongation of quinoxaline-fused porphyrins on the optical, electrochemical, and photovoltaic properties. ZnPBQ showed an intensified Soret band as well as red-shifted Soret and Q bands relative to 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)-6'-carboxylquinoxalino[2,3-b] porphyrinatozinc(II) (ZnPQ), demonstrating the improved light-harvesting property of ZnPBQ. The optical and electrochemical HOMO-LUMO gaps were consistent with those estimated by DFT calculations. The photovoltaic properties were compared under optimized conditions, in which a sealed device structure with TiCl4-treated, TiO2 double layers was used. The ZnPBQ cell exhibited a relatively high power conversion efficiency (eta) of 4.7 %, which was smaller than that of the ZnPQ cell (eta = 6.3 %). The weaker electronic coupling between the LUMO of ZnPBQ and conduction band (CB) of TiO2 or more tilted geometry of ZnPBQ on the TiO2 surface may result in the low electron injection/charge collection efficiency as well as the low incident photon-to-current efficiency (IPCE) for the ZnPBQ cell (maximum IPCE = 56%) relative to the ZnPQ cell (maximum IPCE = 75 %), leading to the lower eta value of the ZnPBQ cell than that of the ZnPQ cell. In addition, the open-circuit potential of the ZnPBQ cell also slightly decreased with the effect of charge recombination from the electrons injected into the CB of TiO2 to I-3(-).

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  • Carbon Nanotube Wiring of Donor-Acceptor Nanograins by Self-Assembly and Efficient Charge Transport Reviewed

    Tomokazu Umeyama, Noriyasu Tezuka, Fumiaki Kawashima, Shu Seki, Yoshihiro Matano, Yoshihide Nakao, Tetsuya Shishido, Masayuki Nishi, Kazuyuki Hirao, Heli Lehtivuori, Nikolai V. Tkachenko, Helge Lemmetyinen, Hiroshi Imahori

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   50 ( 20 )   4615 - 4619   2011.5

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    DOI: 10.1002/anie.201007065

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  • J-aggregation of a sulfonated amphiphilic porphyrin at the air-water interface as a function of pH Reviewed

    Gustavo de Miguel, Kohei Hosomizu, Tomokazu Umeyama, Yoshihiro Matano, Hiroshi Imahori, Marta Perez-Morales, Maria T. Martin-Romero, Luis Camacho

    JOURNAL OF COLLOID AND INTERFACE SCIENCE   356 ( 2 )   775 - 782   2011.4

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    DOI: 10.1016/j.jcis.2011.01.066

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  • 【2011-3】Local stoichiometry in amorphous supramolecular composites analyzed by solid-state C 13 nuclear magnetic resonance Reviewed

    H. Kaji, H. Hayashi, T. Yamada, M. Fukuchi, S. Fujimura, M. Ueda, S. Kang, T. Umeyama, Y. Matano, H. Imahori

    Appl. Phys. Lett.   98 ( 11 )   [113301-1] - [113301-3]   2011.3

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    DOI: 10.1063/1.3565237

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  • Effects of Heterole Spacers on the Structural, Optical, and Electrochemical Properties of 2,5-Bis(1,5-diphenylphosphol-2-yl)heteroles Reviewed

    Yoshihiro Matano, Arihiro Saito, Masato Fujita, Hiroshi Imahori

    HETEROATOM CHEMISTRY   22 ( 3-4 )   457 - 470   2011

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    2,5-Bis(1,5-diphenylphosphol-2-yl)heterole derivatives were prepared via Pd-catalyzed Stille-type cross-coupling reactions of alpha-(tributylstannyl) phosphole or alpha-iodophosphole with the corresponding 2,5-difunctionalized heteroles (pyrrole, furan, and thiophene). X-ray crystallographic analyses of three sigma(4)-P derivatives have elucidated that the coplanar phosphole-heterole-phosphole pi-networks are constructed in both anti-anti and anti-anti conformations. In the case of the pyrrole-linked (sigma(4)-P derivatives, there is a weak hydrogen-bonding interaction between NH and P=X (X = O, S) groups. The optical and electrochemical properties of the sigma(3)-P and sigma(4)-P=O derivatives were revealed experimentally by means of UV-vis absorption/emission spectroscopy and cyclic/differential pulse voltammetry. In all the heterole-linked derivatives, the P-oxidation lowers LUMO levels more efficiently than HOMO levels and, as a result, narrows HOMO-LUMO gaps. In each series (sigma(3)-P or sigma(4)-P=O), the lowest pi-pi* transition energies of the phosphole-heterole-phosphole pi-systems were found to decrease in the following order: thiophene &gt; furan &gt; pyrrole, and their electrochemical oxidation and reduction potentials shift to the negative side in the same order. These results basically reflect the differences in ionization potential and electron affinity of the central heterole spacers. Density functional theory calculations on the model compounds supported the experimentally observed results. The HOMO of the molecule resides on the conjugated polyene network of the pi-system, whereas the LUMO is strongly located on the phosphole subunits. The present comparative study demonstrates, for the first time, that the intriguing electronic structures and the fundamental properties of the 2,5-bis (1,5-diphenylphosphol-2-yl)heteroles can be finely tuned by simple selection of the appropriate heterole spacer. (C) 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:457-470, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20708

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  • Fusion of Phosphole and 1,1 '-Biacenaphthene: Phosphorus(V)-Containing Extended pi-Systems with High Electron Affinity and Electron Mobility Reviewed

    Yoshihiro Matano, Arihiro Saito, Tatsuya Fukushima, Yasuaki Tokudome, Furitsu Suzuki, Daisuke Sakamaki, Hironori Kaji, Akihiro Ito, Kazuyoshi Tanaka, Hiroshi Imahori

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   50 ( 35 )   8016 - 8020   2011

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    DOI: 10.1002/anie.201102782

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  • Photophysics and photoelectrochemical properties of nanohybrids consisting of fullerene-encapsulated single-walled carbon nanotubes and poly(3-hexylthiophene) Reviewed

    Noriyasu Tezuka, Tomokazu Umeyama, Yoshihiro Matano, Tetsuya Shishido, Kaname Yoshida, Tetsuya Ogawa, Seiji Isoda, Kati Stranius, Vladimir Chukharev, Nikolai V. Tkachenko, Helge Lemmetyinen, Hiroshi Imahori

    Energy & Environmental Science   4 ( 3 )   741 - 850   2011

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    DOI: 10.1039/c0ee00482k

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  • Synthesis and photovoltaic properties of thiophene-imide-fused thiophene alternating copolymers with different alkyl side chains Reviewed

    Tomokazu Umeyama, Masaaki Oodoi, Osamu Yoshikawa, Takashi Sagawa, Susumu Yoshikawa, Douvogianni Evgenia, Noriyasu Tezuka, Yoshihiro Matano, Kati Stranius, Nikolai V. Tkachencko, Helge Lemmetyinen, Hiroshi Imahori

    JOURNAL OF MATERIALS CHEMISTRY   21 ( 33 )   12454 - 12461   2011

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    DOI: 10.1039/c1jm11531f

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  • Good Solvent Effects of C-70 Cluster Formations and Their Electron-Transporting and Photoelectrochemical Properties Reviewed

    Noriyasu Tezuka, Tomokazu Umeyama, Yoshihiro Matano, Tetsuya Shishido, Mitsuo Kawasaki, Masayuki Nishi, Kazuyuki Hirao, Heli Lehtivuori, Nikolai V. Ikachenko, Helge Lemmetyinen, Yoshihito Honsho, Shu Seki, Hiroshi Imahori

    JOURNAL OF PHYSICAL CHEMISTRY B   114 ( 45 )   14287 - 14297   2010.11

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    DOI: 10.1021/jp911141s

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  • Synthesis, structures, optical and electrochemical properties, and complexation of 2,5-bis(pyrrol-2-yl)phospholes Reviewed

    Yoshihiro Matano, Masato Fujita, Arihiro Saito, Hiroshi Imahori

    COMPTES RENDUS CHIMIE   13 ( 8-9 )   1035 - 1047   2010.8

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    2,5-Bis(pyrrol-2-yl)phosphole derivatives were prepared using the reaction of titanacycles, generated in situ from a Ti-II reagent and pyrrole-capped 1,6-heptadiynes, with dichloro(phenyl)phosphine. The 2,5-bis(pyrrol-2-yl)phosphole derivatives were found to possess narrower optical HOMO-LUMO gaps and less positive oxidation potentials than those of previously reported 2,5-diarylphosphole analogs. This demonstrates that the intrinsic nature of the electron excessive pyrrole subunits as well as the effective pi-conjugation over the coplanar heterole rings. The sigma(3)-P type 2,5-bis(5-phenylpyrrol-2-yl)phosphole underwent complexation with AuCl(SMe2) and PtCl2 to yield the respective AuCl-monophosphine and PtCl2-bisphosphine complexes. In the square planar Pt-II complex, the pyrrolic NH protons were found to form intramolecular hydrogen bonds with the chlorine atoms that gave rise to symmetrically split, parallel pi-chromophores linked by two Pt-P bonds. Density functional theory calculations on a Pt-II model complex suggested that this cooperative interaction induces a significant split of the original LUMOs of the symmetrical pi-conjugated ligands. (C) 2010 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

    DOI: 10.1016/j.crci.2010.03.017

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  • Effects of π-Elongation and the Fused Position of Quinoxaline-Fused Porphyrins as Sensitizers in Dye-Sensitized Solar Cells on Optical, Electrochemical, and Photovoltaic Properties Reviewed

    Aiko Kira, Yusuke Matsubara, Hiroaki Iijima, Tomokazu Umeyama, Yoshihiro Matano, Seigo Ito, Marja Niemi, Nikolai V. Tkachenko, Helge Lemmetyinen, Hiroshi Imahori

    JOURNAL OF PHYSICAL CHEMISTRY C   114 ( 25 )   11293 - 11304   2010.7

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    DOI: 10.1021/jp1004049

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  • Synthesis of alpha,alpha &apos;-Linked Oligophospholes and Polyphospholes by Using Pd-Cul-Promoted Stille-Type Coupling Reviewed

    Arihiro Saito, Yoshihiro Matano, Hiroshi Imahori

    ORGANIC LETTERS   12 ( 11 )   2675 - 2677   2010.6

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    Palladium-copper-promoted Stille-type cross-coupling reactions between alpha-stannylphospholes and alpha-iodophospholes afforded alpha,alpha&apos;-linked oligophospholes and polyphosphole efficiently. It has been revealed that the polyphosphole P-oxide possesses an extremely narrow band gap and a high electron-accepting ability as compared to polythiophene.

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  • Effects of meso-Diarylamino Group of Porphyrins as Sensitizers in Dye-Sensitized Solar Cells on Optical, Electrochemical, and Photovoltaic Properties Reviewed

    Hiroshi Imahori, Yusuke Matsubara, Hiroaki Iijima, Tomokazu Umeyama, Yoshihiro Matano, Seigo Ito, Marja Niemi, Nikolai V. Tkachenko, Helge Lemmetyinen

    JOURNAL OF PHYSICAL CHEMISTRY C   114 ( 23 )   10656 - 10665   2010.6

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    DOI: 10.1021/jp102486b

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  • Oligothiophene Bearing 1-Hydroxy-1-oxodithieno[2,3-b:3',2'-d]phosphole as a Novel Anchoring Group for Dye-sensitized Solar Cells Reviewed

    Aiko Kira, Yuki Shibano, Soonchul Kang, Hironobu Hayashi, Tomokazu Umeyama, Yoshihiro Matano, Hiroshi Imahori

    CHEMISTRY LETTERS   39 ( 5 )   448 - 450   2010.5

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    DOI: 10.1246/cl.2010.448

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  • Selective Formation and Efficient Photocurrent Generation of [70]Fullerene-Single-Walled Carbon Nanotube Composites Reviewed

    Tomokazu Umeyama, Noriyasu Tezuka, Shu Seki, Yoshihiro Matano, Masayuki Nishi, Kazuyuki Hirao, Heli Lehtivuori, Nikolai V. Tkachenko, Helge Lemmetyinen, Yoshihide Nakao, Shigeyoshi Sakaki, Hiroshi Imahori

    ADVANCED MATERIALS   22 ( 15 )   1767 - 1770   2010.4

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    DOI: 10.1002/adma.200903056

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  • Remarkable effects of p-perfluorophenyl group on the synthesis of core-modified phosphaporphyrinoids and phosphadithiasapphyrin Reviewed

    Takashi Nakabuchi, Yoshihiro Matano, Hiroshi Imahori

    Organic Letters   12 ( 5 )   1112 - 1115   2010.3

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    (Figure Presented) P,X,N2-type phosphaporphyrins and phosphacalixphyrins (X = N, S) bearing a perfluorophenyl (C6F 5) group at the core phosphorus atom were prepared In high overall yield from 1-perfluorophenyl-2,5-di(ethoxycarbonyl)phosphole as a common starting material. In addition, P-C6F5 P,S 2,N2-type sapphyrin was successfully prepared as the first example of ring-expanded phosphorus-containing porphyrin. © 2010 American Chemical Society.

    DOI: 10.1021/ol100114j

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  • Synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes Reviewed

    Yoshihiro Matano, Takashi Nakabuchi, Hiroshi Imahori

    PURE AND APPLIED CHEMISTRY   82 ( 3 )   583 - 593   2010.3

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    Our recent studies on the synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes are summarized. Core-modified P,X,N-2-porphyrins (X = S, N) are accessible from a sigma(4)-phosphatripyrrane and the corresponding 2,5-difunctionalized heteroles in a few steps. X-ray structural analysis of the sigma(3)-P,N-3 porphyrin revealed that it possesses a slightly distorted 18 pi plane. The phosphorus atom incorporated at the core plays an important role in producing unprecedented reactivity and coordinating ability for the porphyrin ring. The P,N-3 free base reacts with [RhCl(CO)(2)](2) in dichloromethane, ultimately yielding an 18 pi P,N-3-rhodium(III) complex, whereas the P,S,N-2 free base undergoes redox-coupled complexation with zero valent group 10 metals to afford the corresponding P,S,N-2-isophlorin-metal(II) complexes. The aromaticity of the free-base porphyrins and the metal complexes was uncovered based on both experimental and theoretical results. It is of particular interest that the P,S,N-2-isophlorin-metal complexes exhibit only a weak antiaromaticity in terms of the magnetic criterion.

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  • Comparison of Cluster Formation, Film Structure, Microwave Conductivity, and Photoelectrochemical Properties of Composites Consisting of Single-Walled Carbon Nanotubes with C60, C70, and C84 Reviewed

    Noriyasu Tezuka, Tomokazu Umeyama, Shu Seki, Yoshihiro Matano, Masayuki Nishi, Kazuyuki Hirao, Hiroshi Imahori

    JOURNAL OF PHYSICAL CHEMISTRY C   114 ( 7 )   3235 - 3247   2010.2

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    DOI: 10.1021/jp910832a

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  • Synthesis and Reactions of Phosphaporphyrins: Reconstruction of pi-Skeleton Triggered by Oxygenation of a Core Phosphorus Atom Reviewed

    Takashi Nakabuchi, Makoto Nakashima, Shinya Fujishige, Haruyuki Nakano, Yoshihiro Matano, Hiroshi Imahori

    JOURNAL OF ORGANIC CHEMISTRY   75 ( 2 )   375 - 389   2010.1

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    (Chemical Equation Presented) The synthesis, structures, optical and redox properties, and reactivity of phosphaporphyrins are reported. The 21-phosphaporphyrin (P,N3-porphyrin) and 23-phospha-21-thiaporphyrin (P,S, N2-porphyrin) were prepared via acid-promoted dehydrative condensation between a phosphatripyrrane and the corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by 2,3-dichloro-5,6- dicyanobenzoquinone oxidation. Experimental (NMR, UV-vis, and X-ray analyses) and theoretical (DFT calculations) results suggest that the 18π aromaticity inherent in regular N4-porphyrins was maintained in these phosphaporphyrins. X-ray crystallography revealed a slightly distorted 18π aromatic ring for the P,N3-porphyrin with the phosphole and three pyrrole rings tilted from the 24-atoms mean plane by 9.6° and 3.8-15.4°, respectively. DFT calculations on model compounds showed that the P,X,N2-porphyrins (X = N, S) possess considerably small HOMO-LUMO gaps as compared with N 4- and S,N3-porphyrins, which is reflected in the red-shifted absorptions, low oxidation potentials, and high reduction potentials of the phosphaporphyrins. The P-oxygenation of the P,X,N2-porphyrins with H2O2 has been found to lead to the formation of different types of products. The 18π P,N3-porphyrin was transformed into the 22π aromatic P(O), N3-porphyrin accompanied by the π extension at the peripheral C3 bridge, whereas the 18π P,S,N2-porphyrin was converted to the isophlorin-type 20π antiaromatic P(O),S,N2-porphyrin. In both of the reactions, simple P-oxygenated 18π P(O),X,N2-porphyrins were formed as the initial products, which were subsequently transformed into the 22π or 20π porphyrins. The two reaction courses from 18π to 20π/22π are apparently determined by the combination of the core heteroatoms (i.e., P,N3 or P,S,N2) and the structure of the peripherally fused carbocycles. The present results demonstrate that the incorporation of a phosphorus atom into the core is not only a highly promising way to modify the fundamental properties of the porphyrin 18π system but also a reliable tool to stabilize uncommon 22π and 20π systems through the chemical modifications at the core phosphorus atom. © 2009 American Chemical Society.

    DOI: 10.1021/jo902060b

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  • Oligothiophene bearing 1-hydroxy-1-oxodithieno[2,3-b:3′,2′-d] phosphole as a novel anchoring group for dye-sensitized solar cells Reviewed

    Aiko Kira, Yuki Shibano, Soonchul Kang, Hironobu Hayashi, Tomokazu Umeyama, Yoshihiro Matano, Hiroshi Imahori

    Chemistry Letters   39 ( 5 )   448 - 450   2010

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    An oligothiophene bearing l-hydroxy-l-oxodithieno[2,3-b:3′,2′- d]phosphole (TP) as a novel anchoring group has been synthesized for dye-sensitized solar cells (DSSC). Attenuated total reflectance-Fourier transform infrared and X-ray photoelectron spectroscopy measurements disclosed the bidentate binding of the phosphinic acid unit to a TiO2 surface. A TPsensitized TiO2 cell yielded a maximum incident photon-tocurrent efficiency of 66% and a power conversion efficiency of 1.8%, indicating that 1-hydroxy-1-oxodithienophosphole is a potential unit as a new type of anchoring groups for DSSC. © 2010 The Chemical Society of Japan.

    DOI: 10.1246/cl.2010.448

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  • Zinc-Induced Fluorescence Enhancement of the 5,10-Porphodimethene-Type Thiophene-Containing Calixphyrins Reviewed

    Yoshihiro Matano, Masato Fujita, Tooru Miyajima, Hiroshi Imahori

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS   185 ( 5-6 )   1098 - 1107   2010

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    The synthesis, structure, and electrochemical/optical properties of the zinc complexes of 5,10-porphodimethene-type thiophene-containing (S,N3-) and phosphole-containing (P,N3-) calixphyrins are reported. The S,N3- and P,N3-calixphyrin free bases react with zinc(II) salts to give the corresponding zinc complexes in good yields. The S,N3-calixphyrin-ZnI complex adopts a distorted square pyramidal geometry, with the S and N atoms at the basal positions. The S,N3-calixphyrin-ZnX complexes emit red fluorescence with fluorescent quantum yields up to 23%, whereas the P,N3-calixphyrin-ZnCl complex is weakly fluorescent. Among the first-row transition metals (Fe2+, Cu2+, and Zn2+) examined, the chelation-enhanced fluorescence is observed specifically for the Zn2+ ion. These results indicate that the 5,10-porphodimethene-type S,N3-hybrid calixphyrin is a promising turn-on fluorescent probe for Zn2+ sensing.

    DOI: 10.1080/10426501003773431

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  • Dispersion of Carbon Nanotubes by Photo- and Thermal-Responsive Polymers Containing Azobenzene Unit in the Backbone Reviewed

    Tomokazu Umeyama, Kazuhiro Kawabata, Noriyasu Tezuka, Yoshihiro Matano, Yuji Miyato, Kazumi Matsushige, Masahiko Tsujimoto, Seiji Isoda, Mikio Takano, Hiroshi Imahori

    CHEMICAL COMMUNICATIONS   46 ( 32 )   5969 - 5971   2010

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    DOI: 10.1039/c0cc00709a

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  • Meso-Substituent Effects on Redox Properties of the 5,10-Porphodimethene-Type P,S,N-2-Hybrid Calixphyrins and Their Metal Complexes Reviewed

    Yoshihiro Matano, Masato Fujita, Tooru Miyajima, Hiroshi Imahori

    ORGANOMETALLICS   28 ( 21 )   6213 - 6217   2009.11

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    DOI: 10.1021/om900745t

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  • Effects of Porphyrin Substituents and Adsorption Conditions on Photovoltaic Properties of Porphyrin-Sensitized TiO2 Cells Reviewed

    Hiroshi Imahori, Shinya Hayashi, Hironobu Hayashi, Akane Oguro, Seunghun Eu, Tomokazu Umeyama, Yoshihiro Matano

    JOURNAL OF PHYSICAL CHEMISTRY C   113 ( 42 )   18406 - 18413   2009.10

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  • New Palladium(II) Complex of P,S-Containing Hybrid Calixphyrin. Theoretical Study of Electronic Structure and Reactivity for Oxidative Addition Reviewed

    Noriaki Ochi, Yoshihide Nakao, Hirofumi Sato, Yoshihiro Matano, Hiroshi Imahori, Shigeyoshi Sakaki

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   131 ( 31 )   10955 - 10963   2009.8

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    The palladium complex of P,S-containing hybrid calixphyrin 1 was investigated with the DFT method. There are two kinds of valence tautomer in 1: one is a Pd(II) form in which the calixphyrin moiety possesses -2 charges and the Pd center takes +2 oxidation state, and the other is a Pd(0) form in which the calixphyrin is neutral and the Pd center takes zero oxidation state. Complex 1 takes the Pd(II) form in the ground state. Though the Pd center takes +2 oxidation state, DFT computations clearly show that the oxidative addition of phenyl bromide (PhBr) to 1 occurs with moderate activation enthalpy, as experimentally proposed. The first step of the oxidative addition is the coordination of PhBr with the Pd center to form intermediate 1INTa, in which the Pd center and the calixphyrin moiety are neutral; in other words, the valence tautomerization from the Pd(II) form to the Pd(0) form occurs in the palladium calixphyrin moiety. The activation enthalpy is 22.5 kcal/mol, and the enthalpy change of reaction is 20.3 kcal/mol. The next step is the C-Br sigma-bond cleavage of PhBr, which occurs with activation enthalpy of 2.0 kcal/mol relative to 1INTa. On the other hand, the oxidative additions of PhBr to palladium complex of P,S-containing hybrid porphyrin 2 and that of conventional porphyrin 3 need much larger activation enthalpies of 49.1 and 74.4 kcal/mol, respectively. The differences in the reactivity among 1, 2, and 3 were theoretically investigated; in 1, the valence tautomerization occurs with moderate activation enthalpy to afford the Pd(0) form which is reactive for the oxidative addition. In 2, the tautomerization from the Pd(II) form to the Pd(0) form needs very large activation enthalpy (43.3 kcal/mol). In 3, such valence tautomerization does not occur at all, indicating that the Pd(II) must change to the Pd(IV) in the oxidative addition of PhBr to 3, which is a very difficult process. These differences are interpreted in terms of the pi* orbital energies of P,S-containing hybrid calixphyrin, hybrid porphyrin, and conventional porphyrin and the flexibility of their frameworks.

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  • Phosphole-Containing Calixpyrroles, Calixphyrins, and Porphyrins: Synthesis and Coordination Chemistry Reviewed

    Yoshihiro Matano, Hiroshi Imahori

    ACCOUNTS OF CHEMICAL RESEARCH   42 ( 8 )   1193 - 1204   2009.8

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  • Phosphole-Triazole Hybrids: A Facile Synthesis and Complexation with Pd(II) and Pt(II) Salts Reviewed

    Yoshihiro Matano, Makoto Nakashima, Arihiro Saito, Hiroshi Imahori

    ORGANIC LETTERS   11 ( 15 )   3338 - 3341   2009.8

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  • Synthesis and Photophysical and Photovoltaic Properties of Porphyrin-Furan and -Thiophene Alternating Copolymers Reviewed

    Umeyama, Tomokazu, Takamatsu, Takeshi, Tezuka, Noriyasu, Matano, Yoshihiro, Araki, Yasuyuki, Wada, Takehiko, Yoshikawa, Osamu, Sagawa, Takashi, Yoshikawa, Susumu, Imahori, Hiroshi

    The Journal of Physical Chemistry C   113 ( 24 )   10798 - 10806   2009.6

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  • Effects of electrode structure on photoelectrochemical properties of ZnO electrodes modified with porphyrin-fullerene composite layers with an intervening fullerene monolayer Reviewed

    H. Hayashi, A. Kira, T. Umeyama, Y. Matano, P. Charoensirithavorn, T. Sagawa, S. Yoshikawa, N.Y. Tkachenko, H. Lemmetyinen, H. Imahori

    Journal of Physical Chemistry C   113 ( 24 )   10819 - 10828   2009.6

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  • Supramolecular Donor-Acceptor Heterojunctions by Vectorial Stepwise Assembly of Porphyrins and Coordination-Bonded Fullerene Arrays for Photocurrent Generation

    Aiko Kira, Tomokazu Umeyama, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda, Jong Kang Park, Dongho Kim, Hiroshi Imahori

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   131 ( 9 )   3198 - +   2009.3

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    A novel strategy for constructing a vertical arrangement of bicontinuous donor-acceptor arrays on a semiconducting electrode has been developed. The relationship between the film structure and the photoelectrochemical properties has been elucidated as a function of the number of donor Layers for the first time. The maximum incident photon-to-current efficiency value (21%) is comparable to the highest value (20%) reported for vertical arrangements of bicontinuous donor-acceptor arrays on electrodes.

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  • A Convenient Method for the Synthesis of α-Ethynylphospholes and Modulation of Their π-Conjugated Systems Reviewed

    Yoshihiro Matano, Makoto Nakashima, Hiroshi Imahori

    Angewandte Chemie International Edition   48 ( 22 )   4002 - 4005   2009

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    DOI: 10.1002/anie.200900542

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  • Acenaphtho[1,2-c]phosphole P-Oxide: A Phosphole-Naphthalene pi-Conjugated System with High Electron Mobility Reviewed

    Arihiro Saito, Tooru Miyajima, Makoto Nakashima, Tatsuya Fukushima, Hironori Kaji, Yoshihiro Matano, Hiroshi Imahori

    CHEMISTRY-A EUROPEAN JOURNAL   15 ( 39 )   10000 - 10004   2009

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    The first comparative study on the optical and electrochemical properties of naphthalene, acenaphthene, and acenaphthylene fused phosphole derivatives, was reported. Naphthalene-, acenaphthene-, and acenaphthylene-fused phosphole derivatives 3-5 were successfully prepared by utilizing a TiII- mediated cyclization of dialkynylated naphthalene (2a), acenaphthene (2b), and acenaphthylene (2c). Treatment of gold(I) complexes 3b,c with excess P(NMe 2)3 afforded o3-P compounds 4b,c, which were subsequently oxidized by m-chloroperbenzoic acid (mCPBA) to the corresponding P-oxides 5b, c. At the last stage of this study, the electron mobility of vacuum-deposited films of 5a and 5b was studied by the time-of-flight (TOF) technique. The results demonstrate that the fusion of the naphthalene ring into the phosphole platform is a highly promising protocol to the development of a new class of phosphole based p-systems with high electron-transporting ability.

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  • Design and synthesis of phosphole-based pi systems for novel organic materials Reviewed

    Yoshihiro Matano, Hiroshi Imahori

    ORGANIC & BIOMOLECULAR CHEMISTRY   7 ( 7 )   1258 - 1271   2009

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  • Remarkable Substituent Effects on the Oxidizing Ability of Tetraarylbismuthonium Tetrafluoroborates in Alcohol Oxidation Reviewed

    Yoshihiro Matano, Takeshi Suzuki, Takaharu Iwata, Tomonori Shinokura, Hiroshi Imahori

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   81 ( 12 )   1621 - 1628   2008.12

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    Substituent effects on the oxidizing ability of tetraarylbismuthonium tetrafluoroborates in alcohol oxidation are reported. Intermolecular and intramolecular competition experiments on geraniol oxidation by the combined use of tetraarylbismuthonium tetrafluoroborates and N,N,N',N'-tetrai-netramethylguanidine (TMG) have revealed that the oxidizing ability of the bismuthonium salt increases by the introduction of methyl groups at the ortho position and an electron-withdrawing group at the para position of the aryl ligands. The intermolecular and intramolecular H/D kinetic isotope effects observed for the competitive oxidation of p-bromobenzyl alcohols have shown that the present oxidation reaction consists of fast pre-equilibrium leading to alkoxytetraarylbismuth(V) intermediates (first step) and alpha-hydrogen abstraction by the aryl ligand attached to the bismuth (second step). The experimental results demonstrate that the electron-deficient aryl ligands enhance the electrophilicity at the bismuth center to put forward the first step and that the bulky ligands destabilize the alkoxybismuth(V) intermediates to accelerate the second step. The newly explored mesityl- and 2,6-xylyltriarylbismuthonium salts have proven to convert primary and secondary alcohols to the corresponding carbonyl compounds with high efficiency under mild conditions. A remark-able steric effect of these oxidants has also been exhibited in the chemoselective oxidation between primary and secondary benzylic alcohols.

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  • Substituent Effects of Porphyrins on Structures and Photophysical Properties of Amphiphilic Porphyrin Aggregates Reviewed

    Kohei Hosomizu, Masaaki Oodoi, Tomokazu Umeyama, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda, Marja Isosomppi, Nikolai V. Tkachenko, Helge Lemmetyinen, Hiroshi Imahori

    JOURNAL OF PHYSICAL CHEMISTRY B   112 ( 51 )   16517 - 16524   2008.12

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  • Synthesis of sterically hindered phthalocyanines and their applications to dye-sensitized solar cells Reviewed

    Seunghun Eu, Takashi Katoh, Tomokazu Umeyama, Yoshihiro Matano, Hiroshi Imahori

    DALTON TRANSACTIONS   2008 ( 40 )   5476 - 5483   2008.10

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    DOI: 10.1039/b803272f

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  • Fused five-membered porphyrin for dye-sensitized solar cells Reviewed

    Shinya Hayashi, Yusuke Matsubara, Seunghun Eu, Hironobu Hayashi, Tomokazu Umeyama, Yoshihiro Matano, Hiroshi Imahori

    CHEMISTRY LETTERS   37 ( 8 )   846 - 847   2008.8

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    Fused five-membered zinc porphyrin carboxylic acid has been synthesized to improve light-harvesting capability in the visible and near-infrared regions. The fused porphyrin-sensitized TiO<SUB>2</SUB> cell exhibited the photocurrent generation extending over 800 nm, although the power conversion efficiency was found to be moderate (0.30%).

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  • Tunable soret-band splitting of an amphiphilic porphyrin by surface pressure Reviewed

    Gustavo de Miguel, Kohei Hosomizu, Tomokazu Umeyama, Yoshihiro Matano, Hiroshi Imahori, Maria T. Martin-Romero, Luis Camacho

    CHEMPHYSCHEM   9 ( 11 )   1511 - 1513   2008.8

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  • Synthesis of thiophene-containing hybrid calixphyrins of the 5,10-porphodimethene type Reviewed

    Yoshihiro Matano, Tooru Miyajima, Noriaki Ochi, Yoshihide Nakao, Shigeyoshi Sakaki, Hiroshi Imahori

    JOURNAL OF ORGANIC CHEMISTRY   73 ( 13 )   5139 - 5142   2008.7

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    The synthesis, structure, and optical and electrochemical properties of thiophene-containing hybrid calixphyrins are reported. The 5,10-porphodimethene type 14 pi- and 16 pi-S,N(2),X-hybrid calixphyrins (X = NH, O, S) were prepared by acid-promoted dehydrative condensation between a thiatripyrrane and the corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by DDQ oxidation. Both crystallographic and spectroscopic analyses of the newly prepared hybrid calixphyrins have revealed that the combination of heteroles explicitly influences the electronic structures of the pi-conjugated framework. The 14 pi-S,N(2),X-hybrid calixphyrins have proven to be fluorescent in solution.

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  • Synthesis, structures, and coordinating properties of phosphole-containing hybrid calixpyrroles Reviewed

    Takashi Nakabuchi, Yoshihiro Matano, Hiroshi Imahori

    ORGANOMETALLICS   27 ( 13 )   3142 - 3152   2008.7

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    Symmetric and asymmetric hybrid calixpyrroles containing a sigma(4)-phosphole or sigma(4)-2,3-dihydrophosphole unit (symmetric and asymmetric sigma(4)-P,N(2),X-hybrids: X = S, O) were prepared by using acid-promoted condensation reactions of the corresponding sigma(4)-phosphatripyrranes with 2,5-bis(1-hydroxy-1-methylethyl)heteroles. The X-ray crystallographic analyses of the symmetric and asymmetric sigma(4)-P,N(2),X-hybrids show that the cavity sizes of the sigma-P,N(2),S-hybrids are larger than those of the sigma(4)-P,N(2),O-hybrids, mainly reflecting the difference in edge-to-edge distances of the thiophene and furan rings. The symmetric sigma(4)-P,N(2),X-hybrids and the asymmetric sigma(4)-P,N(2),S-hybrid were successfully converted to the corresponding sigma(3) forms by reductive desulfurization at the phosphorus center. Each of the symmetric sigma(3)-P,N(2),X-hybrids was obtained as a mixture of two conformers, where the lone pair of the phosphorus atom is located inside (in) and outside (out) the cavity. The interconversion between the in and out type conformers of the asymmetric sigma(3)-P,N(2),S-hybrid was sufficiently slow to isolate each of them. The complexation reactions of the symmetric sigma(3)-P,N(2),S-hybrid with Au(I), Pt(II), and Pd(II) ions afforded both of the in and out type complexes, where the in type complexes were the thermodynamically favored products. In the complexation reactions of the asymmetric sigma(3)-P,N(2), S-hybrids, the stereochemistry at the phosphorus center was retained to give the in or out type complex exclusively. In the in-in type trans-M(II)-bis(phosphine) complexes (M = Pt, Pd) derived from the symmetric and asymmetric sigma(3)-P,N(2),S-hybrids, the M-Cl fragment is bound above the cavities of the two macrocycles. The crystal structures and the (1)H NMR spectra of these M(II) complexes reveal that the P,N(2),S-hybrid calixpyrroles bind the M-Cl fragments through P-M coordination and cooperative NH-Cl hydrogen-bonding interactions.

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  • Triaryl(1-pyrenyl)bismuthonium salts: Efficient photoinitiators for cationic polymerization of oxiranes and a vinyl ether Reviewed

    Yoshihiro Matano, Tomonori Shinokura, Osamu Yoshikawa, Hiroshi Imahori

    ORGANIC LETTERS   10 ( 11 )   2167 - 2170   2008.6

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    Photoirradiation of triaryl(1-pyrenyl)bismuthonium salts in acetonitrile afforded triarylbismuthanes and pyrene, accompanied by the generation of protic acids. Triaryl(1-pyrenyl)bismuthonium hexafluoroantimonates have proven to behave as efficient photoinitiators for cationic polymerization of oxiranes and a vinyl ether, affording the corresponding polymers in good yields within 1 min.

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  • Quinoxaline-fused porphyrins for dye-sensitized solar cells Reviewed

    Seunghun Eu, Shinya Hayashi, Tomokazu Umeyama, Yoshihiro Matano, Yasuyuki Araki, Hiroshi Imahori

    Journal of Physical Chemistry C   112 ( 11 )   4396 - 4405   2008.3

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    5,10,15,20-Tetrakis(2,4,6-trimethylphenyl)-6′-carboxyquinoxalino[2, 3-β]porphyrinatozinc (II) (ZnQMA) and 5,10,15,20-tetrakis(2,4,6- trimethylphenyl)-6′,7′-dicarboxyquinoxalino[2,3-β] porphyrinatozinc (II) (ZnQDA) have been synthesized to evaluate the effects of β,β′-carboxyquinoxalino moieties on the structure and optical, electrochemical, and photovoltaic properties of the porphyrins. Both ZnQMA and ZnQDA exhibited broadened and red-shifted light absorption in UV-visible absorption spectra compared with 5,10,15,20-tetrakis(2,4,6-trimethylphenyl) porphyrinatozinc (II) (ZnP). ZnQMA and ZnQDA also showed decrease in the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap due to the extension of the porphyrin π-system. From the results of 1H NMR spectroscopy and DFT calculations, ZnQMA and ZnQDA were found to adopt saddle and planar structures, respectively. ZnQMA-sensitized TiO 2 solar cell with TiO2 nanoparticles (P25) revealed the power conversion efficiency (η) of 5.2%, whereas ZnQDA-sensitized cell showed η = 4.0%. The superior performance of the ZnQMA-sensitized solar cell to the ZnQDA-sensitized one is originated from both the more favorable electron injection and charge collection efficiency. © 2008 American Chemical Society.

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  • Light Harvesting and Energy Transfer in Multiporphyrin-Modified CdSe Nanoparticles Reviewed

    Soonchul Kang, Masakazu Yasuda, Hiroshi Miyasaka, Hironobu Hayashi, Mitsuo Kawasaki, Tomokazu Umeyama, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda, Hiroshi Imahori

    ChemSusChem   1 ( 3 )   254 - 261   2008.3

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    Multiporphyrin-modified CdSe nanoparticles (CdSe-H2P) were prepared to elucidate the interaction between chromophores and luminescent semiconducting nonoparticles in the excited and ground states. The CdSe-H2P nanoparticles were obtained by place-exchange reactions of hexodecylamine-thiophenol-modified CdSe nanoparticles with porphyrin alkanethiols in toluene. The number of porphyrin molecules on the surface of a single CdSe nanoparticle increased with increasing reaction time to reach a saturated maximum of 21. The porphyrins as well as the core in CdSe-H2P can absorb UV/Vis radiation. Steady-state emission and emission-lifetime measurements reveal efficient energy transfer from the CdSe excited state to the porphyrins in the CdSe-H2P nanoparticles. The resulting porphyrin excited singlet state is not quenched by the CdSe core. These unique properties are in sharp contrast with those of multiporphyrin-modified metal and silica nanoparticles. Thus, semiconducting nanoparticle-multiporphyrin composites ore highly promising as novel artificial photosynthetic materials.

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  • Monophosphaporphyrins: Oxidative pi-extension at the peripherally fused carbocycle of the phosphaporphyrin ring Reviewed

    Yoshihiro Matano, Makoto Nakashima, Takashi Nakabuchi, Hiroshi Imahori, Shinya Fujishige, Haruyuki Nakano

    ORGANIC LETTERS   10 ( 4 )   553 - 556   2008.2

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    The 18π-σ3- and 22π-σ4- phosphaporphyrins were successfully prepared by an acid-promoted condensation between a phosphatripyrrane and a 2,5-bis[hydroxy(phenyl)methyl]pyrrole, and their structures, aromaticity, and optical and electrochemical properties were disclosed. Notably, a σ4-phosphaporphyrinogen and the 18π-σ3-phosphaporphyrin undergo oxidative π-extension at the peripherally fused carbocycle to afford the 22π-σ4- phosphaporphyrin. © 2008 American Chemical Society.

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  • Bithiophene-fused benzo[c]phospholes: Novel P,S-Containing hybrid pi-conjugated systems with small HOMO-LUMO energy gaps Reviewed

    Tooru Miyajima, Yoshihiro Matano, Hiroshi Imahori

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY   2008 ( 2 )   255 - 259   2008.1

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    Bithiophene-fused benzo[c]phospholes were successfully prepared by a TiII-mediated cyclization of dialkynylated bithiophene derivatives. It was revealed that the optical and electrochemical properties of the bithiophene-fused benzo[c]phospholes are deeply related to the π-conjugation modes at the fused bithiophene subunits. Both experimental and theoretical results demonstrate that the appropriately ringannulated systems are potential emitters with small HOMOLUMO energy gaps covering the orange-to-red region due to the efficient π-electron derealization over the three conjugated heterole rings. © Wiley-VCH Verlag GmbH &amp
    Co. KGaA, 2008.

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  • Syntheses, structures, and coordination chemistry of phosphole-containing hybrid calixphyrins: Promising macrocyclic P,N-2,X-mixed donor ligands for designing reactive transition-metal complexes Reviewed

    Yoshihiro Matano, Tooru Miyajima, Noriaki Ochi, Takashi Nakabuchi, Motoo Shiro, Yoshihide Nakao, Shigeyoshi Sakaki, Hiroshi Imahori

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   130 ( 3 )   990 - 1002   2008.1

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  • Redox-Coupled Complexation of 23-Phospha-21-thiaporphyrin with Group 10 Metals: A Convenient Access to Stable Core-Modified Isophlorin Metal Complexes Reviewed

    Yoshihiro Matano, Takashi Nakabuchi, Shinya Fujishige, Haruyuki Nakano, Hiroshi Imahori

    Journal of the American Chemical Society   130 ( 49 )   16446 - 16447   2008

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    Core-modified isophlorin-metal complexes were successfully prepared by redox-coupled complexation of P,S,N2-hybrid porphyrin with zerovalent palladium, nickel, and platinum. In this transformation, the core-phosphorus atom plays crucial roles in enhancing the electron-accepting ability of the 18π porphyrin ring and stabilizing the 20π isophlorin ring owing to high P-M affinity. The isolated Pd and Pt complexes are chemically stable under ambient conditions. The Pd-P,S,N2 isophlorin complex was structurally characterized by X-ray crystallography, which revealed a distorted 20π plane with a square planar palladium(II) center. Experimental (1H, UV-vis, and X-ray) and theoretical (density functional theory calculations) results suggest that the P,S,N2-isophlorin-metal complexes possess nonaromaticity in terms of both magnetic and geometrical criteria. Copyright © 2008 American Chemical Society.

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  • Comparative Study on the Structural, Optical, and Electrochemical Properties of Bithiophene-Fused Benzo[c]phospholes Reviewed

    Yoshihiro Matano, Tooru Miyajima, Tatsuya Fukushima, Hironori Kaji, Yoshifumi Kimura, Hiroshi Imahori

    CHEMISTRY-A EUROPEAN JOURNAL   14 ( 27 )   8102 - 8115   2008

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    Three types of bithiophene-fused benzo[c]phospholes were successfully prepared by Ti(II)-mediated cyclization of the corresponding dialkynylated bithiophene derivatives as a key step. Each sigma(3)-phosphorus center of the benzo[c]phosphole subunits was readily transformed into sigma(4)-phosphorus center by Au coordination or oxygenation. In addition, the bithiophene subunit was functionalized at the alpha,alpha'-carbon atoms by Pd-catalyzed cross-coupling reactions with heteroarylmetals and by an S(N)Ar reaction with hexafluorobenzene. The experimentally observed results (NMR spectroscopy, X-ray analysis, UV/Vis absorption/fluorescence spectroscopy, and cyclic/differential-pulse voltammetry) have revealed that the structural, optical, and electrochemical properties of the bithiophene-fused benzo[c]phospholes vary considerably depending on the pi-conjugation modes at the bithiophene subunits and the substituents of the heterocyclopentadiene components. The appropriately ring-annulated sigma(3)-P derivatives and sigma(4)-P-AuCl complexes were found to emit fluorescence in the orange-red region, and the sigma(4)-P-oxo derivatives proved to undergo reversible one-electron reduction at -1.4 to -1.8V (vs ferrocene/ferrocenium). These results indicate that the bithiophene-fused benzo[c]phospholes possess narrow HOMO-LUMO gaps and low-lying LUMOs, which was confirmed by density functional theory calculations of their model compounds. The time-of-flight measurement of an ITO/benzo[c]phosphole/Al device showed that the electron mobility in the P-oxo derivative is one-order higher than that in Alq(3) at low electric fields. The present study demonstrates that the arene-fused benzo[c]phosphole skeleton could be a highly promising platform for the construction of a new class of phosphole-based optoelectrochemical materials.

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  • Regioselective β-Metalation of meso-Phosphanylporphyrins. Structure and Optical Properties of Porphyrin Dimers Linked by Peripherally Fused Phosphametallacycles Reviewed

    Yoshihiro Matano, Kazuaki Matsumoto, Yoshihide Nakao, Hidemitsu Uno, Shigeyoshi Sakaki, Hiroshi Imahori

    Journal of the American Chemical Society   130 ( 14 )   4588 - 4589   2008

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  • Clusterizatiou, electrophoretic deposition, and photoelectrochemical properties of fullerene-functionalized carbon nanotube composites Reviewed

    Tomokazu Umeyama, Noriyasu Tezuka, Mitsuru Fujita, Shinya Hayashi, Naoki Kadota, Yoshihiro Matano, Hiroshi Imahori

    CHEMISTRY-A EUROPEAN JOURNAL   14 ( 16 )   4875 - 4885   2008

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  • meso-3,5-Bis(trifluoromethyl)phenyl-Substituted Expanded Porphyrins: Synthesis, Characterization, and Optical, Electrochemical, and Photophysical Properties Reviewed

    Soonchul Kang, Hironobu Hayashi, Tomokazu Umeyama, Yoshihiro Matano, Nikolai V. Tkachenko, Helge Lemmetyinen, Hiroshi Imahori

    CHEMISTRY-AN ASIAN JOURNAL   3 ( 12 )   2065 - 2074   2008

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  • Naphthyl-Fused pi -Elongated Porphyrins for Dye-Sensitized TiO2 Cells Reviewed

    Hayashi Shinya, Tanaka Masanobu, Hayashi Hironobu, Eu Seunghun, Umeyama Tomokazu, Matano Yoshihiro, Araki Yasuyuki, Imahori Hiroshi

    Journal of Physical Chemistry C   112 ( 39 )   15576 - 15585   2008

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  • Effects of Porphyrin Substituents on Film Structure and Photoelectrochemical Properties of Porphyrin/Fullerene Composite Clusters Electrophoretically Deposited on Nanostructured SnO2 Electrodes Reviewed

    Hiroshi Imahori, Masahiro Ueda, Soonchul Kang, Hironobu Hayashi, Shnya Hayashi, Hironori Kaji, Shu Seki, Akinori Saeki, Seiichi Tagawa, Tomokazu Umeyama, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda, Motoo Shiro, Nikolai V. Tkachenko, Helge Lemmetyinen

    Chemistry -A European Journal-   13 ( 36 )   10182 - 10193   2007.12

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    DOI: 10.1002/chem.200700446

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  • Hydrogen-bonding effects on film structure and photoelectrochemical properties of porphyrin and fullerene composites on nanostructured TiO2 electrodes Reviewed

    Aiko Kira, Masanobu Tanaka, Tomokazu Umeyama, Yoshihiro Matano, Naoki Yoshimoto, Yi Zhang, Shen Ye, Heli Lehtivuori, Nikolai V. Tkachenko, Helge Lemmetyinen, Hiroshi Imahori

    JOURNAL OF PHYSICAL CHEMISTRY C   111 ( 36 )   13618 - 13626   2007.9

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    DOI: 10.1021/jp0726079

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  • Synthesis of 2-aryl-5-styrylphospholes: Promising candidates for the phosphole-based NLO chromophores Reviewed

    Yoshihiro Matano, Tooru Miyajima, Hiroshi Imahori, Yoshifumi Kimura

    JOURNAL OF ORGANIC CHEMISTRY   72 ( 16 )   6200 - 6205   2007.8

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    DOI: 10.1021/jo070822f

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  • Photoinduced energy transfer in composites of poly[(p-phenylene-1,2-vinylene)-co-(p-phenylene-1,1-vinylidene)] and single-walled carbon nanotubes Reviewed

    Tomokazu Umeyama, Naoki Kadota, Noriyasu Tezuka, Yoshihiro Matano, Hiroshi Imahori

    CHEMICAL PHYSICS LETTERS   444 ( 4-6 )   263 - 267   2007.8

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    DOI: 10.1016/j.cplett.2007.07.013

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  • Electrophoretic Deposition of Single-Walled Carbon Nanotubes Covalently Modified with Bulky Porphyrins on Nanostructured SnO2 Electrodes for Photoelectrochemical Devices Reviewed

    Tomokazu Umeyama, Mitsuru Fujita, Noriyasu Tezuka, Naoki Kadota, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda, Hiroshi Imahori

    Journal of Physical Chemistry C   111 ( 30 )   11484 - 11493   2007.7

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    DOI: 10.1021/jp072075w

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  • Retention of Intrinsic Electronic Properties of Soluble Single-Walled Carbon Nanotubes after a Significant Degree of Sidewall Functionalization by the Bingel Reaction Reviewed

    Tomokazu Umeyama, Noriyasu Tezuka, Mitsuru Fujita, Yoshihiro Matano, Norihiro Takeda, Kei Murakoshi, Kaname Yoshida, Seiji Isoda, Hiroshi Imahori

    Journal of Physical Chemistry   111 ( 27 )   9734 - 9741   2007.6

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    DOI: 10.1021/jp071604t

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  • Electron-donating perylene tetracarboxylic acids for dye-sensitized solar cells Reviewed

    Yuki Shibano, Tomokazu Umeyama, Yoshihiro Matano, Hiroshi Imahori

    ORGANIC LETTERS   9 ( 10 )   1971 - 1974   2007.5

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  • Mesityltriphenylbismuthonium tetrafluoroborate as an efficient bismuth(V) oxidant: remarkable steric effects on reaction rates and chemoselectivities in alcohol oxidation Reviewed

    Yoshihiro Matano, Takeshi Suzuki, Torrionori Shinokura, Hiroshi Imahori

    TETRAHEDRON LETTERS   48 ( 16 )   2885 - 2888   2007.4

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    In the presence of N,N,N',N'-tetramethylguanidine, mesityltriphenylbismuthonium tetrafluoroborate oxidizes primary and secondary alcohols to aldehydes and ketones, respectively, under mild conditions. In this reaction, the mesityl ligand exclusively abstracts an alpha-hydrogen to afford mesitylene and triphenylbismuthane as side products. A remarkable steric effect has also been exhibited in the chemoselective oxidation between primary and secondary alcohols. (c) 2007 Elsevier Ltd. All rights reserved.

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  • Effects of 5-membered heteroaromatic spacers on structures of porphyrin films and photovoltaic properties of porphyrin-sensitized TiO2 cells Reviewed

    Seunghun Eu, Shinya Hayashi, Tomokazu Umeyama, Akane Oguro, Mitsuo Kawasaki, Naoki Kadota, Yoshihiro Matano, Hiroshi Imahori

    Journal of Physical Chemistry C   111 ( 8 )   3528 - 3537   2007.3

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    Novel 5-(5-carboxy-2-thienyl)-10,15,20-tris(2,4,6-trimethylphenyl)- porphyrinatozinc(II) (Zn5S), 5-(5-carboxy-2-furyl)-10,15,20-tris(2,4,6- trimethylphenyl)porphyrinatozinc(II) (Zn5O), and 5-(4-carboxy-2-thieny 1)-10,15,-20-tris(2,4,6-trimethylphenyl)porphyrinatozinc(II) (Zn4S) were synthesized to evaluate the spacer effects on the structures of the porphyrin films and the photovoltaic properties of the porphyrin-sensitized TiO 2 solar cells. Each of the porphyrins showed different adsorption behavior and saturated coverage on the TiO2 surface and photovoltaic properties depending on the identity of heteroatoms in the bridge and the position of carboxylic acid. Specifically, Zn5S-sensitized TiO2 cell displayed larger, maximum incident photon-to-current efficiency of 65% and maximum power conversion efficiency of 3.1% than Zn5O-sensitized TiO2 cell by ∼20% and ∼ 40%, respectively. We interpret that these results are stemmed from ancillary electron-transfer pathway through specific interaction between a sulfur atom in the bridge of Zn5S and the TiO2 surface. Optical spectroscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, density functional theory calculations, and photovoltaic measurements under standard AM 1.5 conditions were employed to support our proposal. © 2007 American Chemical Society.

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  • Synthesis, structures, and properties of meso-phosphorylporphyrins: Self-organization through P-oxo-zinc coordination Reviewed

    Yoshihiro Matano, Kazuaki Matsumoto, Yukiko Terasaka, Hiroki Hotta, Yasuyuki Araki, Osamu Ito, Motoo Shiro, Takahiro Sasamori, Norihiro Tokitoh, Hiroshi Imahori

    CHEMISTRY-A EUROPEAN JOURNAL   13 ( 3 )   891 - 901   2007

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    The synthesis, structures, and optical and electrochemical properties of meso-phosphorylporphyrins are described. The copper-catalyzed carbon-phosphorus cross-coupling reaction of a meso-iodoporphyrin with di-n-butyl phosphite and diphenylphosphane oxide has proved to be an efficient and general method for the synthesis of meso-phosphorylporphyrins. Zinc phosphorylporphyrins thus obtained readily undergo self-organization through Poxo-Zn coordination to form noncovalently linked, cofacial porphyrin dimers or linear olicyomers, which have been characterized by spectroscopic methods and X-ray crystallographic analyses. In toluene, CH2Cl2, and CHCl3, the zinc phosphorylporphyrins exist mostly as dimers or monomers, depending on their concentrations, the temperature, and the presence of additives. The self-association constants for dimerization in toluene have been determined by UV/Vis absorption titration measurements. The meso-diphenylphosphorylporphyrin dimer displays excitonic coupling of the Soret band with a splitting energy of 940 cm(-1). Fluorescence lifetimes of the zinc phosphorylporphyrins have been found to be affected only slightly by the concentration of the solution, and by the addition of triphenylphosphane oxide, suggesting that the effect of dimerization on their photodynamics in the S, state is negligible. On the other hand, the effect of dimerization is clearly reflected in their electrochemical oxidation processes, as the initially produced radical cations are efficiently delocalized over the two porphyrin rings. These findings demonstrate the potential utility of meso-phosphorylporphyrins as new models for the special pair in photosynthesis and as new building blocks for porphyrin-based supramolecular materials.

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  • Electron-Donating Perylene-Tetracarboxylic Acids for Dye-Sensitized Solar Cells Reviewed

    Yuki Shibano, Tomokazu Umeyama, Yoshihiro Matano, Hiroshi Imahori

    Organic Letters   9 ( 10 )   1971 - 1974   2007

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  • Synthesis and aggregation Behavior of meso-sulfinylporphyrins: Evaluation of s-chirality effects on the self-organization to S-oxo-tethered cofacial porphyrin dimers Reviewed

    Yoshihiro Matano, Tomonori Shinokura, Kazuaki Matsumoto, Hiroshi Imahori, Haruyuki Nakano

    CHEMISTRY-AN ASIAN JOURNAL   2 ( 11 )   1417 - 1429   2007

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    The synthesis and aggregation behavior of meso-sulfinylporphyrins are described. The copper-catalyzed C-S cross-coupling reaction of a meso-iodoporphyrin with benzenethiol and n-octanethiol has proved to be an efficient method for the synthesis of meso-sulfanylporphyrins, which are oxygenated by m-chloroperbenzoic acid to produce the corresponding meso-sulfinylporphyrins. Optically active zinc meso-sulfinylporphyrins were successfully isolated by means of optical resolution of the racemates on a chiral HPLC column. Zinc sulfinylporphyrins readily undergo self-organization through S-oxo-zinc coordination to form cofacial porphyrin dimers in solution, in which the hetero- and homodimers are present as a diastereomeric mixture. The aggregation modes of the S-oxo-tethered porphyrin dimers were fully characterized by 1H NMR, IR, and UV/Vis spectroscopy as well as DFT calculations on their model compounds, thus revealing that the self-aggregation behavior depends on the combination of S chirality. The absolute configurations at the sulfur center can be determined by the exciton-coupled CD method. The observed self-association constant for the S-oxo-tethered dimerization of (S)-phenylsulfinylporphyrin in toluene is larger than that in dichloromethane, which reflects the difference in dipole moments between the homodimer and the monomer. In cyclic and differential pulse voltammetry, the first oxidation process of the cofacial dimers is split into two reversible steps, which indicates that the initially produced π radical cations are delocalized efficiently between the two porphyrin rings. The present findings demonstrate the potential utility of meso-sulfinyl groups as promising ligands for investigating the effects of peripheral chirality on the structures and optical and electrochemical properties of metal-assisted porphyrin self-assemblies. © 2007 Wiley-VCH Verlag GmbH &amp
    Co. KGaA, Weinheim.

    DOI: 10.1002/asia.200700191

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  • Novel unsymmetrically pi-elongated porphyrin for dye-sensitized TiO2 cells

    Masanobu Tanaka, Shinya Hayashi, Seunghun Eu, Tomokazu Umeyama, Yoshihiro Matano, Hiroshi Imahori

    CHEMICAL COMMUNICATIONS   ( 20 )   2069 - 2071   2007

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  • Large Reorganization Energy of Pyrrolidine-Substituted Perylenediimide in Electron Transfer Reviewed

    Shibano, Yuki, Umeyama, Tomokazu, Matano, Yoshihiro, Tkachenko, Nikolai V, Lemmetyinen, Helge, Araki, Yasuyuki, Ito, Osamu, Imahori, Hiroshi

    Journal of Physical Chemistry C   111 ( 16 )   6133 - 6142   2007

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    DOI: 10.1021/jp068893q

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  • Synthesis of a phosphorus-containing hybrid porphyrin Reviewed

    Yoshihiro Matano, Takashi Nakabuchi, Tooru Miyajima, Hiroshi Imahori, Haruyuki Nakano

    ORGANIC LETTERS   8 ( 25 )   5713 - 5716   2006.12

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    A phosphorus-containing hybrid porphyrin was successfully prepared via the BF3-promoted dehydrative condensation between sigma(4)-phosphatripyrrane and 2,5-bis[hydroxy(phenyl)methyl]thiophene. The NMR and UV-vis absorption spectra, electrochemical measurements, and DFT calculations revealed that the sigma(3)-P,N-2,S-hybrid porphyrin exhibits high aromaticity as an 18 pi-electron system in terms of both geometric and magnetic criteria.

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  • Comparison of electrode structures and photovoltaic properties of porphyrin-sensitized solar cells with TiO2 and Nb, Ge, Zr-added TiO2 composite electrodes Reviewed

    Hiroshi Imahori, Shinya Hayashi, Tomokazu Umeyama, Seunghun Eu, Akane Oguro, Soonchul Kang, Yoshihiro Matano, Tetsuya Shishido, Supachai Ngamsinlapasathian, Susumu Yoshikawa

    LANGMUIR   22 ( 26 )   11405 - 11411   2006.12

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    DOI: 10.1021/la061527d

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  • Phosphorus-containing hybrid calixphyrins: Promising mixed-donor ligands for visible and efficient palladium catalysts Reviewed

    Yoshihiro Matano, Tooru Miyajima, Takashi Nakabuchi, Hiroshi Imahori, Noriaki Ochi, Shigeyoshi Sakaki

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   128 ( 36 )   11760 - 11761   2006.9

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    DOI: 10.1021/ja0640039

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  • Synthesis and photophysical properties of electron-rich perylenediimide-fullerene dyad Reviewed

    Yuki Shibano, Tomokazu Umeyama, Yoshihiro Matano, Nikolai V. Tkachenko, Helge Lemmetyinen, Hiroshi Imahori

    ORGANIC LETTERS   8 ( 20 )   4425 - 4428   2006.9

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    DOI: 10.1021/ol061506a

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  • Ordered Supramolecular Assembly of Porphyrin-Fullerene Composites on Nanostructured SnO2 Electrodes Reviewed

    S. Kang, T. Umeyama, M. Ueda, Y. Matano, H. Hotta, K. Yoshida, S. Isoda, M. Shiro, H. Imahori

    Advanced Materials   18 ( 19 )   2549 - 2552   2006.9

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    DOI: 10.1002/adma.200600312

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  • A convenient method for the synthesis of 2,5-difunctionalized phospholes bearing ester groups Reviewed

    Yoshihiro Matano, Tooru Miyajima, Takashi Nakabuchi, Yuichiro Matsutani, Hiroshi Imahori

    JOURNAL OF ORGANIC CHEMISTRY   71 ( 15 )   5792 - 5795   2006.7

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    Symmetrically and unsymmetrically 2,5-difunctionalized phospholes bearing ester groups were prepared in a one-pot procedure from the corresponding diynes and dichloro-(phenyl) phosphine via titanacyclopentadienes. The observed optical properties of the functionalized phospholes show that the pi-conjugative push-pull interaction between the 2- and 5-substituents plays an important role in controlling the light-emitting efficiency.

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  • Structure and photoelectrochemical properties of phthalocyanine and perylene diimide composite clusters deposited electrophoretically on nanostructured SnO(2) electrodes Reviewed

    Aiko Kira, Tomokazu Umeyama, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda, Marja Isosomppi, Nikolai V. Tkachenko, Helge Lemmetyinen, Hiroshi Imahori

    LANGMUIR   22 ( 12 )   5497 - 5503   2006.6

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    Clusters of phthalocyanine and phthalocyanine-perylene diimide have been prepared and electrophoretically deposited on nanostructured SnO(2) electrodes. The structure and photoelectrochemical properties of the clusters have been investigated by using UV-visible absorption, dynamic light scattering (DLS), atomic force microscopy (AFM), transmission electron microscopy (TEM), and photoelectrochemical and photodynamical measurements. Enhancement of the photocurrent generation efficiency in the composite system has been achieved relative to that in the phthalocyanine reference system without the perylene diimide. Such information will be valuable for the design of molecular photoelectrochemical devices that exhibit efficient photocurrent generation.

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  • Phosphole-containing hybrid calixpyrroles: New multifunctional macrocyclic ligands for platinum(II) ions Reviewed

    Yoshihiro Matano, Takashi Nakabuchi, Tooru Miyajima, Hiroshi Imahori

    ORGANOMETALLICS   25 ( 13 )   3105 - 3107   2006.6

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    DOI: 10.1021/om060300a

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  • A Photoelectrochemical Device with a Nanostructured SnO2 Electrode Modified with Composite Clusters of Porphyrin-Modified Silica Nanoparticle and Fullerene Reviewed

    Hiroshi Imahori, Keigo Mitamura, Yuki Shibano, Tomokazu Umeyama, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda, Yasuyuki Araki, Osamu Ito

    The Journal of Physical Chemistry B   110 ( 23 )   11399 - 11405   2006.5

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    DOI: 10.1021/jp061524+

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  • Structure and photoelectrochemical properties of nanostructured SnO(2) electrodes deposited electrophoretically with the composite clusters of porphyrin-modified gold nanoparticle with a long spacer and fullerene Reviewed

    H Imahori, A Fujimoto, S Kang, H Hotta, K Yoshida, T Umeyama, Y Matano, S Isoda

    TETRAHEDRON   62 ( 9 )   1955 - 1966   2006.2

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    Structure and photoelectrochemical properties of nanostructured SnO(2) electrodes deposited electrophoretically with the composite clusters of porphyrin-modified gold nanoparticle with a long, flexible spacer and C(60) molecules have been examined to obtain basic information on the development of organic solar cells with a high performance. The photoelectrochemical system with the long, flexible spacer between the porphyrin and the gold nanoparticle in the porphyrin-modified gold nanoparticle exhibited comparable external quantum yield in the UV-vis regions relative to porphyrin-modified gold nanoparticle with a relatively short spacer-C(60) Composite reference system. These results demonstrate that a suitable spacer to incorporate C(60) molecules efficiently between the porphyrins in porphyrin-modified gold nanoparticles is a prerequisite for improving the performance of porphyrin and fullerene-based organic solar cells. (c) 2005 Elsevier Ltd. All rights reserved.

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  • Efficient photocurrent generation by SnO2 electrode modified electrophoretically with composite clusters of porphyrin-modified silica microparticle and fullerene Reviewed

    H Imahori, K Mitamura, T Umeyama, K Hosomizu, Y Matano, K Yoshida, S Isoda

    CHEMICAL COMMUNICATIONS   ( 4 )   406 - 408   2006.1

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    A silica microparticle has been successfully employed as a nanoscaffold to self-organize porphyrin and C-60 molecules on a nanostructured SnO2 electrode which exhibits efficient photocurrent generation.

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  • Structure and Photoelectrochemical Properties of Phthalocyanine and Perylene Diimide Composite Clusters Deposited Electrophoretically on Nanostructured SnO2 Electrodes Reviewed

    Aiko Kira, Tomokazu Umeyama, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda, Marja Isosomppi, Nikolai V. Tkachneko, Helge Lemmetyinen, Hiroshi Imahori

    Langmuir   22 ( 12 )   5497 - 5503   2006

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    DOI: 10.1021/la0533314

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  • Host-guest interactions in the supramolecular incorporation of fullerenes into tailored holes on porphyrin-modified gold nanoparticles in molecular photovoltaics Reviewed

    H Imahori, A Fujimoto, S Kang, H Hotta, K Yoshida, T Umeyama, Y Matano, S Isoda, M Isosomppi, NV Tkachenko, H Lemmetyinen

    CHEMISTRY-A EUROPEAN JOURNAL   11 ( 24 )   7265 - 7275   2005.12

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    Novel gold nanoparticles modified with a mixed self-assembled monolayer of porphyrin alkanethiol and short-chain alkanethiol were prepared (first step) to examine the size and shape effects of surface holes (host) on porphyrin-modified gold nanoparticles. ne porphyrin-modified gold nanoparticles with a size of about 10 nm incorporated C-60 molecules (guest) into the large, bucket-shaped holes, leading to the formation of a supramolecular complex of porphyrin-C-60 composites (second step). Large composite clusters with a size of 200400 nm were grown from the supramolecular complex of porphyrin-C-60 composites in mixed solvents (third step) and deposited electrophoretically onto nanostructured SnO2 electrodes (fourth step). Differences in the porphyrin:C-60, ratio were found to affect the structures and photoelectrochemical properties of the composite clusters in mixed solvents as well as on the SnO2, electrodes. The photoelectrochemical performance of a photoelectrochemical device consisting of SnO2 electrodes modified with the porphyrin-C-60 composites was enhanced relative to a reference system with small, wedged-shaped surface holes on the gold nanoparticle, Time-resolved transient absorption spectroscopy with fluorescence lifetime measurements suggest the occurrence of ultrafast electron transfer from the porphyrin excited singlet states to C-60 or the formation of a partial charge-transfer state in the composite clusters of supramolecular complexes formed between porphyrin and C-60 leading to efficient photocurrent generation in the system. Elucidation of the relationship between host-guest interactions and photoelectrochemical function in the present system will provide valuable information on the design of molecular devices and machines including molecular photo-voltaics.

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  • Effects of fullerene substituents on structure and photoelectrochemical properties of fullerene nanoclusters electrophoretically deposited on nanostructured SnO2 electrodes Reviewed

    H Hotta, S Kang, T Umeyama, Y Matano, K Yoshida, S Isoda, H Imahori

    JOURNAL OF PHYSICAL CHEMISTRY B   109 ( 12 )   5700 - 5706   2005.3

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    Two kinds of fullerene derivatives have been designed to examine the effect of the fullerene substituents on the structure and photoelectrochemical properties of fullerene clusters electrophoretically deposited on nanostructured SnO2 electrodes. The cluster sizes increase and the incident photon-to-current efficiencies decrease with introduction of large substituents into C-60. The trend for photocurrent generation efficiency as well as surface morphology on the electrode can be explained by the steric bulkiness around the C-60 molecules. A C-60 molecule with two alkoxy chains is suggested to give a bilayer vesicle structure, irrespective of the hydrophobic nature of both the C-60 and alkoxy chain moieties. Such information will be valuable for the design of photoactive molecules, which are fabricated onto electrode surfaces to exhibit high energy conversion efficiency.

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  • Molecular Photoelectrochemical Devices: Supramolecular Incorporation of C60 Molecules into Tailored Holes on Porphyrin-Modified Gold Nanoclusters Reviewed

    Hiroshi Imahori, Atsushi Fujimoto, Soonchul Kang, Hiroki Hotta, Kaname Yoshida, Tomokazu Umeyama, Yoshihiro Matano, Seiji Isoda

    Advanced Materials   17 ( 14 )   1727 - 1730   2005

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    DOI: 10.1002/adma.200401770

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  • Hydrogen Bonding Effects on the Surface Structure and Photoelectrochemical Properties of Nanostructured SnO2 Electrodes Modified with Porphyrin and Fullerene Composites Reviewed

    Hiroshi Imahori, Jia-Chen Liu, Hiroki Hotta, Aiko Kira, Tomokazu Umeyama, Yoshihiro Matano, Guifeng Li, Shen Ye, Marja Isosomppi, Nikolai V. Tkachenko, Helge Lemmetyinen

    The Journal of Physical Chemistry B   109 ( 39 )   18465 - 18474   2005

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    DOI: 10.1021/jp0537409

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  • Effects of Fullerene Substituents on Structure and Photoelectrochemical Properties of Fullerene Nanoclusters Electrophoretically Deposited on Nanostructured SnO2 Electrodes Reviewed

    Hiroki Hotta, Soonchul Kang, Tomokazu Umeyama, Yoshihiro Matano, Kaname Yoshida, Seiji Isoda, Hiroshi Imahori

    The Journal of Physical Chemistry B   109 ( 12 )   5700 - 5706   2005

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  • Host-Guest Interactions in the Supramolecular Incorporation of Fullerenes into Tailored Holes on Porphyrin-Modified Gold Nanoparticles in Molecular Photovoltaics Reviewed

    Hiroshi Imahori, Atsushi Fujimoto, Soonchul Kang, Hiroki Hotta, Kaname Yoshida, Tomokazu Umeyama, Yoshihiro Matano, Seiji Isoda, Marja Isosomppi, Nikolai V. Tkachenko, Helge Lemmetyinen

    Chemistry-A European Journal   11 ( 24 )   7265 - 7275   2005

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    DOI: 10.1002/chem.200500610

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  • Remarkable substituent effects on the oxidizing ability of triarylbismuth dichlorides in alcohol oxidation Reviewed

    Y Matano, T Hisanaga, H Yamada, S Kusakabe, H Nomura, H Imahori

    JOURNAL OF ORGANIC CHEMISTRY   69 ( 25 )   8676 - 8680   2004.12

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    DOI: 10.1021/jo0485740

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  • Diverse structures and remarkable oxidizing ability of triarylbismuthane oxides. Comparative study on the structure and reactivity of a series of triarylpnictogen oxides Reviewed

    Y Matano, H Nomura, T Hisanaga, H Nakano, M Shiro, H Imahori

    ORGANOMETALLICS   23 ( 23 )   5471 - 5480   2004.11

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    A systematic series of triarylbismuthane oxides was prepared in order to disclose their structure and reactivity, which have been compared with those of lighter pnictogen counterparts. X-ray crystallographic analysis of tris(2-methoxyphenyl)bismuthane oxide and tris(2-methoxyphenyl)stibane oxide revealed that they exist as dimers with a flat bis(a-oxo) ring, implying that the polarized Bi+-O- and Sb+-O- bonds aggregate to attain electrostatic stabilization. In sharp contrast to their phosphorus, arsenic, and antimony counterparts, triarylbismuthane oxides are thermally unstable and possess a high oxidizing ability. In particular, the bismuthane oxides bearing ortho-substituted aryl ligands oxidized primary and secondary alcohols to aldehydes and ketones, respectively, with high efficiency under mild conditions.

    DOI: 10.1021/om0494115

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  • A new, efficient method for direct alpha-alkenylation of beta-dicarbonyl compounds and phenols using alkenyltriarylbismuthonium salts Reviewed

    Y Matano, H Imahori

    JOURNAL OF ORGANIC CHEMISTRY   69 ( 16 )   5505 - 5508   2004.8

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    DOI: 10.1021/jo0492721

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  • Substituent effects of porphyrin monolayers on the structure and photoelectrochemical properties of self-assembled monolayers of porphyrin on indium-tin oxide electrode Reviewed

    H Imahori, K Hosomizu, Y Mori, T Sato, TK Ahn, SK Kim, D Kim, Y Nishimura, Yamazaki, I, H Ishii, H Hotta, Y Matano

    JOURNAL OF PHYSICAL CHEMISTRY B   108 ( 16 )   5018 - 5025   2004.4

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    Self-assembled monolayers (SAMs) of porphyrins have been prepared to examine the substituent effects of porphyrin monolayers on the structure and photoelectrochemical properties of the SAMs on an ITO electrode. The ultraviolet (UV)-visible absorption, steady-state fluorescence, and cyclic voltammetry measurements for the porphyrin SAMs revealed that the interaction between the porphyrins without bulky tert-butyl groups is much larger than that of the porphyrins with bulky tert-butyl groups. Photoelectrochemical measurements were performed in nitrogen-saturated Na2SO4 aqueous solution containing triethanolamine as an electron sacrificer using the modified ITO working electrode, a platinum wire counter electrode, and an Ag/AgCl reference electrode. The internal quantum yields of photocurrent generation together with the porphyrin fluorescence lifetimes rernain virtually the same irrespective of the steric hindrance, which is in sharp contrast with severe self-quenching of the porphyrin excited singlet state in conventional molecular assemblies such as Langmuir-Blodgett films. The two-dimensional, densely packed structure of the porphyrins in SAM is responsible for the long-lived excited singlet state, which is similar to the antenna function of photosystem I in cyanobacteria. These results will provide valuable information on the construction of artificial light-harvesting systems.

    DOI: 10.1021/jp037625e

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  • Hydrogen bonding effect on photocurrent generation in porphyrin fullerene photoelectrochemical devices Reviewed

    H Imahori, JC Liu, K Hosomizu, T Sato, Y Mori, H Hotta, Y Matano, Y Araki, O Ito, N Maruyama, S Fujita

    CHEMICAL COMMUNICATIONS   ( 18 )   2066 - 2067   2004

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    A hydrogen bonding effect on photocurrent generation has been evaluated successfully in a mixed film of porphyrin and fullerene with hydrogen bonding on an ITO electrode, which exhibits efficient cathodic photocurrent generation as compared to the reference system without hydrogen bonding.

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  • Nanostructured artificial photosynthesis

    Hiroshi Imahori, Yukie Mori, Yoshihiro Matano

    Journal of Photochemistry and Photobiology C: Photochemistry Reviews   4 ( 1 )   51 - 83   2003.4

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    We have proposed a novel strategy for artificial photosynthesis where porphyrins and fullerenes are assembled as building blocks into nanostructured artificial photosynthetic systems by the help of self-assembled monolayers. Photodynamical studies on porphyrin-fullerene-linked systems revealed that fullerenes accelerate photo-induced electron transfer and charge-shift and slow down charge recombination, which is in sharp contrast with the modalities of conventional two-dimensional aromatic acceptors such as quinones and imides. We proposed and demonstrated, for the first time, that such electron transfer properties are attributable to the small reorganization energies of fullerenes, which make it possible to optimize artificial photosynthetic multistep charge separation. The multistep electron transfer strategy was combined with our finding that fullerenes have small reorganization energies, which are well-suited for the construction of light energy conversion systems as well as artificial photosynthetic models. Highly efficient photosynthetic energy and electron transfers were realized at gold and indium-tin oxide (ITO) electrodes modified with self-assembled monolayers of porphyrin-fullerene-linked systems. Porphyrin-modified gold nanoclusters were found to have potential as artificial photosynthetic materials and photonic molecular devices. These results provide basic principles and concepts for the development of nanostructured artificial photosynthetic materials as well as molecular devices. © 2003 Japanese Photochemistry Association. Published by Elsevier Science B.V. All rights reserved.

    DOI: 10.1016/S1389-5567(03)00004-2

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  • Synthesis and structural comparison of triaryl(sulfonylimino)pnictoranes Reviewed

    Yoshihiro Matano, Hazumi Nomura, Hitomi Suzuki

    Inorganic Chemistry   41 ( 7 )   1940 - 1948   2002.4

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    Triarylphosphanes 1 (Ar3P
    Ar = Ph, 4-MeC6H4), triphenylarsane (2), and triarylstibanes 3 (Ar3Sb
    Ar = 2-MeC6H4, 2-MeOC6H4) reacted with trifluoromethanesulfonamide (7a) in the presence of equimolar diethyl azodicarboxylate to afford the corresponding triaryl(sulfonylimino)pnictoranes [Ar3M=NSO2CF3
    8 (M = P), 9 (M = As), 10 (M = Sb)]. The Kirsanov-type reaction of triarylantimony dichlorides 5 (Ar3SbCl2
    Ar = 2-MeC6H4, 2-MeOC6H4) and triarylbismuth dichlorides 6 (Ar3BiCl2
    Ar = 2-MeC6H4, 2-MeOC6H4, 2,4,6-Me3C6H2) with sulfonamides 7 (H2NSO2R
    R = CF3, 4-MeC6H4, Me) in the presence of 2 equiv of potassium tert-butoxide yielded triaryl(sulfonylimino)-λ5-stibanes 10 and -bismuthanes 11, respectively. The ortho-substitution in aryl ligands of 10 and 11 has been found to bring about considerable kinetic stabilization of the reactive Sb=N and Bi=N bonds. A structural comparison was made for a series of triaryl(sulfonylimino)pnictoranes 8-11 by IR spectroscopy and X-ray crystallography. In the IR spectra of 9-11, SO2 asymmetric stretching absorptions (νSO2) were observed at lower wavenumbers as compared to those of phosphorus counterparts 8. The difference in frequency (δνSO2) from 8 increased progressively as the pnictogen element being utilized moved down the group 15 column on the periodic table. X-ray crystallographic analyses of eight of the triaryl(sulfonylimino)pnictoranes prepared confirmed the increasing single-bond character of the M=N bond, with the contribution from the canonical structure M+-N=S(O)-O- increasing in importance in the order P &lt
    As &lt
    Sb &lt
    Bi. Among all triaryl(sulfonylimino)pnictoranes examined, only imino-λ5-bismuthanes 11 oxidized alcohols to carbonyl compounds.

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  • New syntheses of bismuthonium salts, bismuthonium ylides and bismuthane imides using triarylbismuth(V)-oxo and -hydroxo compounds Reviewed

    Y Matano, H Nomura

    SYNTHESIS-STUTTGART   ( 5 )   631 - 634   2002.4

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    Triarylbismuth(V)-oxo and -hydroxo compounds react with organoboronic acids and esters in the presence of (BF3OEt2)-O-. to afford the corresponding bismuthonium salts. They also undergo dehydrative coupling with cyclic 1,3-dicarbonyl compounds, amides and sulfonamides to give stabilized bismuthonium ylides, bismuthane N-acylimides and bismuthane N-sulfonylimides, respectively. All reactions proceed efficiently under mild conditions.

    DOI: 10.1055/s-2002-23536

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  • Synthesis and Structural Comparison of Triaryl(sulfonylimino)pnictoranes Reviewed

    Yoshihiro Matano, Hazumi Nomura, Hitomi Suzuki

    Inorganic Chemistry   41 ( 7 )   1940 - 1948   2002

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    DOI: 10.1021/ic0110575

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  • Facile Oxidation of Alcohols to Carbonyl Compounds Using a Tris(2-methylphenyl)bismuth Dichloride–DBU Binary System Reviewed

    Yoshihiro Matano, Hazumi Nomura

    Angewandte Chemie International Edition   41 ( 16 )   3028 - 3031   2002

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    High efficiency and chemoselectivity as well as the facile isolation of the carbonyl products by simple workup procedures characterize a new method of alcohol oxidation. A variety of primary and secondary alcohols are oxidized to aldehydes and ketones by the combined use of tris(2-methylphenyl)bismuth dichloride and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) under mild conditions [Eq. (1)].

    DOI: 10.1002/1521-3773(20020816)41:16<3028::AID-ANIE3028>3.0.CO;2-U

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  • Synthesis, structure, and reactions of (acylimino)triaryl-λ5-bismuthanes: First comparative study of the (acylimino)pnictorane series Reviewed

    Y. Matano, H. Nomura, H. Suzuki, M. Shiro, H. Nakano

    Journal of the American Chemical Society   123 ( 44 )   10954 - 10965   2001.11

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    The synthesis, structure, and reactions of (acylimino)triaryl-λ5-bismuthanes and a comparative study of the structure and reactivity of a series of (acylimino)pnictoranes are reported. Treatment of ortho-substituted triarylbismuth dichlorides 1 (Ar3BiCl2
    Ar = 2-MeC6H4, 2-MeOC6H4, 2,4,6-Me3C6H2) with amides 2 (H2-NCOR
    R = CF3, CCl3, 3,5-(CF3)2C6H3) in the presence of 2.2 equiv of KO-t-Bu in dichloromethane afforded (acylimino)triaryl-λ5-bismuthanes 3 (Ar3Bi=NCOR) in yields of 77-96%. The ortho-substituted aryl ligands and the electron-withdrawing N-substituents afford kinetic and thermodynamic stabilization, respectively, to the reactive Bi=N bond. The structures and properties of a series of (acylimino)pnictoranes (Ar3M=NCOR and H3M=NCOCF3
    M = P, As, Sb, Bi) are compared by IR and 13C and 15N NMR, X-ray crystallography, and ab initio molecular orbital calculations. It was found that the contribution of the M+-N=C-O- canonical form becomes more prominent and the single-bond character of the M=N bond increases progressively as the pnictogen atom becomes heavier. The Bi=N bond of (acylimino)-λ5-bismuthanes 3 possesses a highly polarized single-bond character, probably due to the differences in orbital size and electronegativity between the bismuth and nitrogen atoms. Thermal decomposition of (aroylimino)triaryl-λ5-bismuthane 3f (o-Tol3Bi=NCOAr
    Ar = 3,5-(CF3)2C6H3) produces a gel in dry conditions or aniline 12 (ArNH2) in slightly wet conditions with a good recovery of tris(2-methylphenyl)bismuthane (4a). It is likely that the aryl isocyanate 13 (ArNCO) is produced during the thermolysis via a concerted C → N migration of the Ar group with an elimination of the triarylbismuthonio group as bismuthane 4a. (Acylimino)triaryl-λ5-bismuthanes 3 oxidize 1,1,2,2-tetraphenylethanediol, benzenethiol, methanol, and ethanol to benzophenone, diphenyl disulfide, methyl formate, and acetaldehyde, respectively, in two different reaction pathways depending on the structure of the substrates. Compound 3d (o-Tol3Bi=NCOCCl3) transfers the nitrenoid moiety to triphenylphosphane, triphenylarsane, and tris(2-methylphenyl)stibane to give the corresponding (acylimino)pnictoranes (Ar3M=NCOCl3
    M = P, As, Sb) and 4a, suggesting that 3d is thermodynamically much less stable than their lighter pnictogen counterparts. The copper-catalyzed decomposition of 3 (o-Tol3Bi=NCOR) afforded N-acyl-o-toluidines 18 (o-TolNHCOR) via a Bi → N migration of the tolyl group. The observed reactivities of (acylimino)triaryl-λ5-bismuthanes 3 demonstrate a good leaving ability of the bismuthonio group.

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  • Organic Chemistry Created by Bismuth : Syntheses and Applications

    MATANO Yoshihiro

    J. Synth. Org. Chem. Jpn.   59 ( 9 )   4 - 14   2001.9

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    The syntheses and reactions of bismuthonium salts and bismuth ylides are reported. Various types of bismuthonium salts bearing a Bi-C<I><SUB>sp</SUB></I><I><SUP>3</SUP></I>, Bi-C<I><SUB>sp</SUB></I><I><SUP>2</SUP></I>, or Bi-C<I><SUB>sp</SUB></I> bond have been prepared by the Lewis-acid promoted reaction of triphenylbismuth difluoride with organometallic reagents. The bismuthonium salts thus obtained behave as alkyl cation equivalents, alkenyl cation equivalents, and carbene precursors. The bismuth ylides bearing a carbonyl group at the ylidic carbon react with carbonyl compounds to undergo epoxidation, transposition, or ring expansion depending on the structure of the substrates employed. These reaction modes are characteristic of bismuth among the group 15 elements. The stabilized bismuth ylides bearing a highly cross-conjugated ylidic carbon decompose, at an elevated temperature or in the presence of a copper catalyst, to give trisubstituted oxazoles. The observed unique reactivities of the bismuthonium salts and the bismuth ylides are ascribed to the good leaving ability of the triarylbismuthonio group.

    DOI: 10.5059/yukigoseikyokaishi.59.834

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  • A new synthesis of triarylbismuthanes via directed ligand coupling of oxazoline-substituted tetraarylbismuthonium salts: Synthesis of polystyrenes bearing the diarylbismuthino group Reviewed

    Y Matano, SA Begum, H Suzuki

    SYNTHESIS-STUTTGART   ( 7 )   1081 - 1085   2001.6

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    Triarylbismuthanes bearing a vinyl, formyl, or acetyl group have been prepared in good yield via the directed ligand coupling of oxazoline-substituted tetraarylbismuthonium salts. Radical polymerization of the resulting diaryl(4-vinylphenyl)bismuthanes produced bismuth-containing polystyrenes soluble in organic solvents.

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  • Dimeric Triarylbismuthane Oxide: A Novel Efficient Oxidant for the Conversion of Alcohols to Carbonyl Compounds Reviewed

    Yoshihiro Matano, Hazumi Nomura

    Journal of the American Chemical Society   123 ( 26 )   6443 - 6444   2001

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    DOI: 10.1021/ja010584k

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  • Stabilized bismuthonium ylides bearing a highly cross-conjugated ylidic carbon atom: synthesis, structures, and reactions Reviewed

    Y Matano, H Nomura, H Suzuki

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   611 ( 1-2 )   89 - 99   2000.10

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    The reaction of iminotriaryl-lambda(5)-bismuthanes (2; Ar3Bi=NR; R = COR " or SO2R ") with dialkyl acetylenedicarboxylates (3; R'O2CC=CCO2R') has been found to afford highly stabilized bismuthortium ylides (4; Ar3Bi=C(CO2R')-C(CO2R')=NR) in 50-92% yield. The X-ray crystallographic analyses of two of these ylides demonstrated that their bismuth center possesses a distorted tetrahedral geometry with the highly cross-conjugated ylidic carbon atom. The observed Bi-C-ylide bond lengths of 2.178(7)-2.199(7) Angstrom are close to ordinary Bi-C-Ar bond lengths, suggesting an appreciable single bond character of the Bi-C-ylide bond. The action of two equivalents of acetic acid, hydrogen chloride, or 4-nitrophenol on 4 cleaved the Bi-C-ylide bond to give the corresponding triarylbismuth(V) compounds of the type Ar3BiX2 and olefins (5; R'O2CCH=C(CO2R')NHR). 4-Nitrobenzenethiol was oxidized by 0.5 equivalents of 4 to give bis(4-nitrophenyl) disulfide with a good recovery of triarylbismuthane 6 and olefin 5. On thermolysis at 200 degrees C, or when decomposed in the presence of a copper catalyst at room temperature, the ylides 4 bearing an N-aroyl group gave 2,4,5-trisubstituted oxazoles 7 and triarylbismuthanes 6 in moderate to excellent yields. (C) 2000 Elsevier Science S.A. All rights reserved.

    DOI: 10.1016/S0022-328X(00)00295-3

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  • Tp* rhenium(V) oxo-halide, -hydride, -alkyl, -phenyl, and -alkoxide complexes: Syntheses and oxidations Reviewed

    Y Matano, TO Northcutt, J Brugman, BK Bennett, S Lovell, JM Mayer

    ORGANOMETALLICS   19 ( 14 )   2781 - 2790   2000.7

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    Rhenium-oxo complexes with the hydridotris(3,5-dimethyl-1-pyrazolyl)borate (Tp*) ligand are described. Halide complexes Tp*Re(O)X(Cl) (X = Cl, I) are prepared by treatment of Tp*Re(O)(OH)Cl with HX. Reaction of Tp*Re(O)Cls (3) with 1 or 2 equiv of LiPh/ZnCl2 or Et2Zn produces the corresponding oxo-aryl and oxo-alkyl complexes Tp*Re(O)(Ph)Cl, Tp*Re(O)(Ph)(2), and Tp*Re(O)(Et)Cl. Alkoxide complexes Tp*Re(O)(OR)CI and Tp*Re(O)(OR)(2) are prepared from 3 and ROH, PhOH, or catechol, Triflate complexes Tp*Re(O)X(OTf) (X = halide, H, Et, Ph, Oft, OPh) have been prepared by halide metathesis with AgOTf or by alkoxide metathesis with Me3SiOTf. Hydride complexes Tp*Re(O)(H)X (X = Cl, H) are generated from the corresponding alkoxide complexes with BH3. THF. Oxidation of Tp*Re(O)Ph(OTf) with Me2SO gives a phenoxide complex, and oxidation of Tp*Re(O)Et(OTf) with pyridine N-oxide gives acetaldehyde, Both reactions are similar to oxidations of related Tp compounds. Tp*Re(O)H(OTf) is oxidized by either reagent to Tp*Re(O)(3), with liberation of H+; such a hydride complex has not been accessible in the Tp system. The Tp* ligand imparts added stability to the rhenium(V) derivatives, making preparations easier. Steric constraints of the Tp* ligand are illustrated by the lack of phenyl and pyridine ligand rotation on the NMR time scale. The stability and crowding of the Tp* compounds inhibits reactions with oxygen atom donors so that heating is often required, and the resulting oxidations are more complex than for analogous Tp compounds.

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  • Synthesis, structure, and reactions of triaryl(methyl)bismuthonium salts Reviewed

    Y Matano

    ORGANOMETALLICS   19 ( 12 )   2258 - 2263   2000.6

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    Treatment of triarylbismuth difluorides 2 (Ar3BiF2; a, Ar = Ph; b, Ar = 4-MeC6H4; c, Ar = 4-MeOC6H4; d,Ar = 2-MeOC6H4) with methylboronic acid (3) in the presence of BF3. OEt2 in CH2Cl2 afforded the corresponding triaryl(methyl)bismuthonium tetrafluoroborates 4a-d ([Ar3MeBi+][BF4-]) in 42-91% yield. X-ray crystallographic analysis of compound 4d revealed that the bismuth center possesses a distorted tetrahedral geometry with C-Bi-C bond angles of 106.1(3)-113.6(3)degrees and Bi-C bond lengths of 2.182(7)-2.195(8) Angstrom. Compound 4a transferred the methyl group to Ph3E (E = P, As, Sb), tris(4-methylphenyl)bismuthine, ROH (R = Me, Et, i-Pr, PhCH2), water, sodium benzenesulfinate, sodium benzoate, N,N-dimethylformamide (DMF), and thioacetamide to give the corresponding methylated products with a good recovery of triphenylbismuthine. The pseudo-first-order rate constant (k(obsd) = 2.9 x 10(-4) s(-1)) observed for the reaction between 4a and benzyl alcohol (5d) was about twice as large as that (k(obsd) = 13 X 10(-4) s(-1)) between MeOTf and 5d (in CDCl3 at 23 degrees C; [4a] or [MeOTf] = 0.062 M; [5d] = 0.97 M). The observed reactivity of 4a clearly demonstrates the high nucleofugality of the triphenylbismuthonio group.

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  • Synthesis and first x-ray structural analysis of monomeric imino-λ5-stibanes Reviewed

    Yoshihiro Matano, Hazumi Nomura, Hitomi Suzuki

    Inorganic Chemistry   39 ( 7 )   1340 - 1341   2000.4

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    Triaryl (trifluoromethylsulfonylimino)-λ5-stibanes (Ar3-Sb=NSO2CF3) were prepared by the Kirsanov-type reaction of triarylantimony dichlorides with CF3SO2NH2 in the presence of KO-t-Bu and by the redox condensation of triarylstibines with CF3SO2NH2 in the presence of diethyl azodicarboxylate. The Sb = N bond of these monomeric imino-λ5-stibanes was found to possess moderate single-bond character owing to the resonance hybridization with the electron-withdrawing N-sulfonyl group.

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  • First synthesis of alkynyltriphenylbismuthonium salts and their dual reaction modes in sulfonylation Reviewed

    Y Matano

    CHEMICAL COMMUNICATIONS   ( 22 )   2233 - 2234   2000

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    Treatment of triphenylbismuth difluoride with alkynyldiisopropoxyboranes in the presence of BF3. OEt2 in CH2Cl2 gives alkynyltriphenylbismuthonium tetrafluoroborates, which react with sodium p-toluenesulfinate in dual reaction modes depending on the solvents employed.

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  • Electrochemical and reactivity comparisons among isoelectronic oxo, imido, and nitrido complexes of rhenium and osmium Reviewed

    BK Bennett, TJ Crevier, DD DuMez, Y Matano, WS McNeil, JM Mayer

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   591 ( 1-2 )   96 - 103   1999.12

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    Cyclic voltammetry has been used to study the electrochemical properties of 29 isoelectronic and isostructural osmium(VI)-nitrido, rhenium(lr)-oxo, and rhenium(V)-imido complexes of the form Tp(()*M-)(E)(X)(Y) [Tp(()*()) = Tp, HB(pz)(3); or Tp*, HB(3,5-Me(2)pz)(3)]. Oxidations from d(2) to d(1) species are typically reversible or quasi-reversible, while reductions to d(3) species are usually irreversible. The E-1/2 values for oxidation vary from &gt; + 2 V for TpOs(N)(Cl)(2) to - 0.11 V for TpRe(Ntolyl)(Ph)(Me) (vs. Cp2Fe+ , 0 in MeCN/(Bu4NPF6)-Bu-n). The potentials follow simple trends, Os(N) &gt; Re(O) &gt; Re(Ntolyl) and Tp &gt; Tp*. Potentials for TpM(E)(X)(Y) are also affected by the X and Y ligands, with OTf &gt; Cl congruent to I &gt; Ph &gt; alkyl, correlating with the Hammett a values for X and Y. In contrast, peak potentials for reduction of the compounds (ca. - 1.0 to - 1.5 V) do not follow simple patterns. The reactivity of these complexes as inner-sphere oxidants does not correlate with their peak reduction potentials. Rather. the ease of oxidation of the compounds better parallels their reactivity as oxidants. (C) 1999 Elsevier Science S.A. All rights reserved.

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  • Synthesis and stereochemical behavior of unsymmetrical tetraarylbismuthonium salts Reviewed

    Y Matano, SA Begum, T Miyamatsu, H Suzuki

    ORGANOMETALLICS   18 ( 26 )   5668 - 5681   1999.12

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    The synthesis and stereochemical behavior of unsymmetrical tetraarylbismuthonium salts were investigated. Two methods (tin and boron methods) for synthesizing unsymmetrically substituted tetraarylbismuthonium salts were developed. In the tin method, successive treatment of triarylbismuth difluorides (1; (Ar3BiF2)-Bi-1) with trimethylsilyl cyanide and aryltri-n-butylstannanes (2; Bu3SnAr2) in the presence of a Lewis acid (BF3. OEt2 or Me3SiOTf) in boiling dichloromethane afforded tetraarylbismuthonium salts (3, [(Ar3ArBi+)-Ar-1-Bi-2][BF4-], or 5, [(Ar3ArBi+)-Ar-1-Bi-2][OTf-]) in 44-85% yield. In contrast, in the boron method, similar treatment of 1 with arylboronic acids (4; (ArB)-B-2(OH)(2)) in the presence of BF3. OEt2 afforded the tetrafluoroborates 3 in 55-99% yield at room temperature. Both methods were used to synthesize unsymmetrical tetraarylbismuthonium salts (9; (ArArArArBi+)-Ar-1-Ar-2-Ar-3-Bi-4][BF4-]) starting from unsymmetrical triarylbismuth difluorides 8. The boron method was also used. to synthesize unsymmetrical tetraarylbismuthonium tetrafluoroborates 14 bearing an oxazoline group at the ortho position ([(4-MeOC6H4)(4-CF3C6H4)(2-OxC(6)H(4))ArBi+][BF4-]; Ox = 4,4-dimethyl-3,4-dihydrooxazol-2-yl; a, Ar = 4-MeC6H4; b, Ar = 2-C4H3S). The reaction of bismuthonium tetrafluoroborate 14b with ammonium tosylate afforded bismuthonium tosylate 15, which, on treatment with sodium halides, was converted to the corresponding halides 16 ([(4-MeOC6H4)(4-CF3C6H4)(2-OxC(6)H(4))(2-C4H3S)Bi+][X-]; a, X = Cl; b, X = Br; c, X = I). Tetrafluoroborates 14 and tosylate 15 are thermally stable, but halides 16 are unstable and underwent ligand coupling in solution. The X-ray diffraction analysis of a tetrafluoroborate 20 ([(4-MeC6H4)(3)(2-OxC(6)H(4))Bi+][BF4-]) revealed a distorted tetrahedral geometry at the bismuth center, which was coordinated by the neighboring oxazoline nitrogen atom. The stereochemical behavior of the synthesized bismuthonium salts was investigated, The signals due to the diastereotopic geminal methyl groups on the oxazoline ring of 14 and 15 did not coalesce in the H-1 NMR spectra in 1,2;dichlorobenzene-d(4) (up to 150 degrees C), in DMSO-d(6) (up to 135 degrees C), and in pyridine-d(5) (up to 110 degrees C), whereas those of chloride 16a and bromide 16b coalesced in pyridine-d(5), 1,2-dichlorobenzene-d(4), chlorobenzene-d(5), and toluene-d(8). The coalescence temperature (T-c) depended on the nucleophilicity of the counteranions as well as on the polarity of the solvents; T-c decreased as the nucleophilicity of the counteranions increased or as the polarity of the solvent decreased. Thus, the configuration at bismuth in tetrafluoroborates 14 and tosylate 15 was found to be stable, whereas that in halides 16 strongly depended on the solvent polarity.
    The observed permutation of bismuthonium halides, [(ArArArArBi+)-Ar-1-Ar-2-Ar-3-Bi-4][X-], can be explained by a pseudorotation mechanism involving a nonionic pentacoordinate species of the type (ArArArArBiX)-Ar-1-Ar-2-Ar-3-Bi-4.

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  • Synthesis and reactivity of aryl- and alkyl-rhenium(V) imido-triflate compounds: An unusual mechanism for triflate substitution Reviewed

    WS McNeil, DD DuMez, Y Matano, S Lovell, JM Mayer

    ORGANOMETALLICS   18 ( 18 )   3715 - 3727   1999.8

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    Treatment of the d(2) rhenium tolylimido complex TpRe(NTol)X-2 with RMgX, RLi, or organozinc reagents yields TpRe(NTol)(R)X [R = Ph, Me,-Et, i-Pr, n-Bu; X = Cl or I; Tol = p-tolyl; Tp = hydrotris(1-pyrazolyl)borate] or TpRe(NTol)R-2 (R = Ph, Me). Iodide for triflate metathesis with AgOTf yields TpRe(NTol)(X)OTf [X = Ph, Et, Cl, OTf (=OSO2CF3)]. Reaction of TpRe(NTol)(Et)I with excess rather than stoichiometric AgOTf generates the ethylene hydride cation [TpRe(NTol)(eta(2)-C2H4)(H)][OTf], which slowly rearranges by ethylene insertion to form TpRe(NTol)(Et)OTf. Treatment of TpRe(NTol)(Ph)I with AgPF6 gives not iodide abstraction but rather [{TpRe(NTol)(Ph)I}(2)Ag][PF6], with two Re-I-Ag linkages. Excess pyridine (py) slowly displaces triflate in TpRe(NTol)Ph(OTf) (11) to give [TpRe(NTol)Ph(py)][OTf]. The reaction is first-order in 11 and first-order in py. Triflate substitution is similarly slow in the oxo-Tp* derivative, Tp*Re(O)Ph(OTf) [Tp* = HB(3,5-Me(2)pz)(3)]. These reactions are many orders of magnitude slower than substitution in the oxo-Tp derivative TpRe(O)Ph(OTf). Kinetic and mechanistic data rule out dissociation of triflate ion in or before the rate-determining step and are most consistent with an associative pathway, Reaction with 1,10-phenanthroline gives the k(2)-Tp complex [K-2-TpRe(NTOl)Ph(phen)][OTf], indicating the lability of one arm of the Tp ligand. TpRe(NTol)Ph-2, TpRe(NTol)Me-2, TpRe(NTol)(Ph)OTf, TpRe(NTol)(OTf)(2), [{TpRe(NTol)(Ph)I}(2)Ag][PF6], and [K-2-TpRe(NTol)Ph(phen)] [OTf] have been structurally characterized. The imido ligand is a better electron donor and has a smaller trans influence than an oxo group in this system.

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  • First synthesis, structure, and reactivity of (acylimino)triaryl-lambda(5)-bismuthanes stabilized by ortho-substituted aryl ligands Reviewed

    Y Matano, H Nomura, M Shiro, H Suzuki

    ORGANOMETALLICS   18 ( 14 )   2580 - 2582   1999.7

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    The reactive Bi(V)=N bond in (acylimiao)triaryl-lambda(5)-bismuthanes has been found to be stabilized effectively by ortho-substituted aryl ligands such as o-tolyl, o-anisyl, and mesityl groups, These imino-lambda(5)-bismuthanes, in which the bismuth center possesses a distorted tetrahedral geometry, behave-as ct nitrene precursor as well as an oxidizing agent, depending on the substrates and conditions.

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  • Reactions of triphenylbismuthonium 2-oxoalkylides with 1,2-dicarbonyl compounds

    MM Rahman, Y Matano, H Suzuki

    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1   ( 11 )   1533 - 1541   1999.6

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    Triphenylbismuthonium 2-oxoalkylides 2, generated in situ from bismuthonium salts 1 and a base in THF at low temperature, react with alpha-keto esters 3 and alpha-dikerones 6 to give oxiranes 4 or 7 and/or O-aroyl enolates of unsymmetrical beta-diketones 8, depending on the structures of substrates. Similar treatment of 2 with o-quinones 10 results in the ring expansion to 2-acyl-3-hydroxytropones 11. The enolates 8 and tropones 11 are most likely to be formed via the 1,2-carbon-to-oxygen and carbon-to-carbon migrations of the acyl group, respectively, both under simultaneous elimination of the triphenylbismuthonio group as bismuthine 5. Tropone 11c readily condenses with hydrazine hydrate to give a functionalized pyrazole 18.

    DOI: 10.1039/A900751B

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  • An alternative ring expansion mode of acenaphthenequinone to hydroxyphenalenone Reviewed

    MM Rahman, Y Matano, H Suzuki

    SYNTHESIS-STUTTGART   1999 ( 3 )   395 - 397   1999.3

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    Treatment of acenaphthenequinone with triphenylbismuthonium 2-oxoalkylides in THF at low temperature results in the C-insertion between two carbonyl functions, giving the corresponding 2-acyl-3-hydroxyphenalenones in good yield.

    DOI: 10.1055/s-1999-3407

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  • Fluoride Reactions with Hydrotris(pyrazolyl)borate Rhenium Oxo Complexes: Re–F vs. B–F Bond Formation Reviewed

    Darin D. DuMez, Todd, O. Northcutt, Yoshihiro Matano, James M. Mayer

    Inorganic Chemistry   38 ( 14 )   3309 - 3312   1999

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    DOI: 10.1021/ic981334g

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  • Synthesis and Reactivity of Aryl- and Alkyl-Rhenium(V) Imido-Triflate Compounds: An Unusual Mechanism for Triflate Substitution Reviewed

    W. Stephen McNeil, Darin D. DuMez, Yoshihiro Matano, Scott Lovell, James M. Mayer

    Organometallics   18 ( 18 )   3715 - 3727   1999

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    DOI: 10.1021/om980914i

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  • Synthesis and Reactions of Bismuthonium Salts and Ylides Bearing an α-Ester Group Reviewed

    Yoshihiro Matano, M. Mizanur Rahman, Masanori Yoshimune, Hitomi Suzuki

    The Journal of Organic Chemistry   64 ( 18 )   6924 - 6927   1999

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    DOI: 10.1021/jo990690t

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  • First Synthesis, Structure, and Reactivity of (Acylimino)triaryl-λ5-bismuthanes Stabilized by Ortho-Substituted Aryl Ligands Reviewed

    Yoshihiro Matano, Hazumi Nomura, Motoo Shiro, Hitomi Suzuki

    Organometallics   18 ( 14 )   2580 - 2582   1999

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    DOI: 10.1021/om990252c

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  • A new and efficient method for the preparation of bismuthonium and telluronium salts using aryl- and alkenylboronic acids. First observation of the chirality at bismuth in an asymmetrical bismuthonium salt Reviewed

    Y Matano, SA Begum, T Miyamatsu, H Suzuki

    ORGANOMETALLICS   17 ( 20 )   4332 - 4334   1998.9

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    Treatment of triarylbismuth difluorides with aryl- and alkenylboronic acids in the presence of BF3. OEt2 afforded tetraaryl- and alkenyltriarylbismuthonium tetrafluoroborates, respectively, while similar treatment of diphenyltellurinyl difluoride yielded the corresponding telluronium salts. The chirality at bismuth was observed for the first time from the H-1 NMR spectrum of an asymmetrical bismuthonium salt.

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  • Water-soluble non-ionic triarylbismuthanes. First synthesis and properties Reviewed

    Y Matano, Y Aratani, T Miyamatsu, H Kurata, K Miyaji, S Sasako, H Suzuki

    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1   ( 16 )   2511 - 2517   1998.8

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    The synthesis and properties of some new water-soluble non-ionic triarylbismuthanes are described. o-, m- and p-Tris(methoxymethoxyphenyl)bismuthanes 1a-c are prepared from BiCl3 and the corresponding organolithium or Grignard reagents. Oxidative chlorination of 1a-c with SO2Cl2 affords tris(methoxymethoxyphenyl)bismuth dichlorides 2a-c, which are deprotected by aqueous HCl to give tris(hydroxyphenyl)bismuth dichlorides 3a-c. Treatment of tris(3-hydroxyphenyl)bismuth dichloride 3b with NH2NH2 yields tris(3-hydroxyphenyl)bismuthane 5, which dissolves in dilute aqueous NaOH. N,N-Bis(2-tert-butyl-dimethylsiloxyethyl)benzenesulfonainide, prepared from benzenesulfonyl chloride and silyl-protected diethanolamine, is ortho-lithiated and reacted with 1/3 equiv. of BiCl3 to give Ar3Bi 9a {Ar = 2-[N,N-bis-(2-tert-butyldimethylsiloxyethyl)sulfamoyl]phenyl}. m-Phenylene-bridged Bi-2- and Bi-3-polybismuthanes 12 and 13 are prepared by the reaction between ortho-lithiated 9a and Ar2BiI 10, Desilylation of 9a, 12 and 13 by Bu4NF or p-TsOH . H2O in EtOH leads to the corresponding bismuthanepolyols 11, 14 and 15, The reaction between benzene-1,3-disulfonamide 16 bearing the silyl-protected bis(2-hydroxyethyl)amino side chains and 1/3 equiv. of BiCl3 affords tris{2,4-bis[N,N-bis(2-tert-butyldimethylsiloxyethyl)sulfamoyl]phenyl}bismuthane 17, which is deprotected by p-TsOH . H2O to yield tris{2,4-bis[N,N-bis(2-hydroxyethyl)sulfamoyl]phenyl}bismuthane 18, Compounds 11, 14 and 15 are only slightly soluble in water, but compound 18 is fairly soluble.

    DOI: 10.1039/A803946A

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  • Synthesis and reactions of rhenium(V) oxo-hydride complexes Reviewed

    Yoshihiro Matano, Seth N. Brown, Todd O. Northcutt, James M. Mayer

    Organometallics   17 ( 14 )   2939 - 2941   1998.7

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    Tp*ReO(H)Cl, TpRe(O)H(Cl), and Tp*ReO-(H)2 have been prepared by alkoxide-for-hydride metathesis using BH3·THF. The inflate derivative Tp*Re(O)H-(OTf) inserts olefins and is oxidized by oxygen-atom transfer reagents to give HOTf and Tp*ReO3, likely by a pathway involving hydride migration to an oxo ligand (Tp* = hydrotris(3,5-dimethyl-1-pyrazolyl)borate
    triflate = OTf = OSO2CF3).

    DOI: 10.1021/om980184e

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  • A New and Efficient Method for the Preparation of Bismuthonium and Telluronium Salts Using Aryl- and Alkenylboronic Acids. First Observation of the Chirality at Bismuth in an Asymmetrical Bismuthonium Salt Reviewed

    Yoshihiro Matano, Shameem A. Begum, Takashi Miyamatsu, Hitomi Suzuki

    Organometallics   17 ( 20 )   4332 - 4334   1998

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    DOI: 10.1021/om9804531

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  • Synthesis and Reaction of Unsymmetrical Tetraarylbismuthonium Salts. First Isolation of Bismuthonium Salts Bearing All Different Aryl Groups Reviewed

    Yoshihiro Matano, Takashi Miyamatsu, Hitomi Suzuki

    Chemistry Letters   27 ( 2 )   127 - 128   1998

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    Successive treatment of triarylbismuth difluorides (1) with a Lewis acid, Me3SiCN, and aryltributylstannanes (2) in CH2Cl2 gives unsymmetrical tetraarylbismuthonium salts (3) in moderate to good yield. The migratory aptitude of an aryl ligand in [Ph3ArBi+][BF4 -] (3a, b) in the C-arylation of 2-naphthol is Ph&gt
    p-Tol&gt
    p-Ans.

    DOI: 10.1246/cl.1998.127

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  • Reaction of Triphenylbismuthonium 2-Oxoalkylides with Benzils. A Novel One-pot Conversion of Symmetrical α-Diketones into O-Aroyl Enolates of Unsymmetrical β-Diketones Reviewed

    M. Mizanur Rahman, Yoshihiro Matano, Hitomi Suzuki

    Chemical Communications   ( 13 )   1359 - 1360   1998

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    DOI: 10.1039/a801879k

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  • Synthesis and Properties of a Series of Phenylene-Bridged Bin-Bismuthanes Reviewed

    Yoshihiro Matano, Haruto Kurata, Toshihiro Murafuji, Nagao Azuma, Hitomi Suzuki

    Organometallics   17 ( 18 )   4049 - 4059   1998

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    DOI: 10.1021/om980411c

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  • Sodium diarylbismuthide as a reagent for the bismuthanation of reactive arenes. Application to the synthesis of mixed triarylbismuthanes bearing a substituent group incompatible with Grignard and organolithium reagents Reviewed

    Mizanur Rahman, Yoshihiro Matano, Hitomi Suzuki

    Organometallics   16 ( 15 )   3565 - 3568   1997.7

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    Several mixed triarylbismuthanes bearing an electron-withdrawing functionality, such as the nitro, carbonyl, or ester group, which are inaccessible by the conventional methods based on organometallic reagents such as Grignard and organolithium compounds, are synthesized in low to acceptable yields by the reaction of in situ generated sodium diarylbismuthide with iodoarenes or arenediazonium tetrafluoroborates.

    DOI: 10.1021/om9701377

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  • First Synthesis and Properties of Dendritic Bin-Bismuthanes Reviewed

    Hitomi Suzuki, Haruto Kurata, Yoshihiro Matano

    Chemical Communications   ( 23 )   2295 - 2296   1997

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    Directed tris-ortholithiation of tris[2-(diethylaminosulfonyl)phenyl]bismuthane 1 with tert-butyllithium followed by treatment with 3 equiv. of bis[2-(diethylaminosulfonyl)-phenyl]bismuth iodide 2a gives a symmetrically branched Bi4-bismuthane 5a, which, on a similar treatment, is converted in a one-pot synthesis into a highly branched Bi10-bismuthane 6a.

    DOI: 10.1039/a706338e

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  • A new general method for the preparation of unsymmetrical telluronium salts Reviewed

    Yoshihiro Matano, Hitomi Suzuki, Nagao Azuma

    Organometallics   15 ( 17 )   3760 - 3765   1996.8

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    A new general approach to a variety of unsymmetrical telluronium salts has been developed. Treatment of diaryltellurinyl difluorides 1 with silyl enol ethers 2 in the presence of BF3·OEt2 gave (2-oxoalkyl)diaryltelluronium tetrafluoroborates 3 in quantitative yield. When a siloxycyclopropane, an allylsilane, a benzylstannane, an alkenylstannane, an alkynylsilane, or an arylstannane was used in place of compound 2, the corresponding 3-oxoalkyl-, allyl-, benzyl-, alkenyl-, and alkynyldiaryltelluronium tetrafluoroborates as well as the unsymmetrically triarylated telluronium salt were obtained in good yields. The 125Te chemical shifts of these compounds span over the range δ 645-755 ppm, which were in accordance with the onium nature of the tellurium center. An X-ray structural analysis of 3a clearly showed that the central tellurium atom has a distorted-pyramidal structure with a weak coordinative interaction between the tellurium and carbonyl oxygen atoms. The telluronium salt [Ph2TeCH2CH2C(=O)Bu-t]+[BF 4]- easily transferred its alkyl moiety to a sulfinate anion to form the corresponding alkyl phenyl sulfone and diphenyl telluride, while the base-promoted reaction of [Ph2TeCH2C(=O)Ph]+[BF4]- with benzaldehyde afforded a chalcone and diphenyl telluroxide.

    DOI: 10.1021/om960320k

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  • First synthesis, X-ray structure analysis and reactions of alkenyltriphenylbismuthonium salts Reviewed

    Y Matano, M Yoshimune, N Azuma, H Suzuki

    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1   ( 16 )   1971 - 1977   1996.8

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    Treatment of triphenylbismuth difluoride with alkenyltrimethylsilanes 1 or trimethylsilyl cyanide-alkenyltrialkylstannanes 3 in the presence of boron trifluoride-diethyl ether gave the corresponding alkenyltriphenylbismuthonium tetrafluoroborates 2 in moderate to good yields, An X-ray crystallographic analysis of the salt 2e confirmed the distorted tetrahedral geometry of the central bismuth atom, When treated with a sulfinate 5 or the thiolate 11, the salts 2 readily transferred both the vinyl and phenyl moieties to these nucleophiles to afford the sulfones 7-10 or the sulfides 12, 13, respectively, In the presence of a palladium catalyst, the salt 2e underwent the Heck-type reaction with ethyl acrylate 17 to afford the dienoate 18 and cinnamate 19 in moderate yields, Action of KOBu(t) on the salt 2b yielded p-tolylacetylene 22, while a similar reaction with the salt 2e in the presence of the styrenes 23 gave the cyclopropanes 24, A Hammett study of the latter reaction has suggested a possible involvement of an alkylidenecarbene as the intermediate in these base-promoted reactions.

    DOI: 10.1039/P19960001971

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  • A new convenient synthesis of triarylbismuthanes bearing three different aryl groups by the grignard arylation of unsymmetrical diarylbismuth triflate-hexamethylphosphoric triamide (HMPA) complexes Reviewed

    Yoshihiro Matano, Takashi Miyamatsu, Hitomi Suzuki

    Organometallics   15 ( 7 )   1951 - 1953   1996.4

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    Triarylbismuthanes bearing three different aryl groups, Ar1Ar2Ar3Bi (4), have been conveniently synthesized by the action of aryl Grignard reagent Ar3-MgBr on unsymmetrical diarylbismuth triflate-HMPA complexes Ar1Ar2BiOTf(HMPA)2 (8), which are readily accessible by the selective cleavage of triarylbismuthanes Ar12Ar2Bi (7
    Ar1 is more fugacious than Ar2) with trimethylsilyl triflate in the presence of HMPA.

    DOI: 10.1021/om9509709

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  • Reaction of a moderately stabilized bismuthonium ylide with 1,2-dicarbonyl compounds. A novel ring enlargement of ortho-quinones to 3-hydroxytropones Reviewed

    Yoshihiro Matano, Hitomi Suzuki

    Chemical Communications   ( 24 )   2697 - 2698   1996

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    Triphenylbismuthonium 2-oxoalkylide 2, generated in situ from salt 1 in THF at low temperature, readily reacts with 1,2-dicarbonyl compounds 3 to give 2,3-diacyloxiranes 4 or 2-acyl-3-hydroxytropones 5 depending on the structure of the electrophiles involved.

    DOI: 10.1039/cc9960002697

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  • A new aspect of organobismuth chemistry: Synthesis, properties, and reactions of bismuthonium compounds Reviewed

    Yoshihiro Matano, Hitomi Suzuki

    Bulletin of the Chemical Society of Japan   69 ( 10 )   2673 - 2681   1996

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    This article is intended to describe recent progress in the chemistry of bismuthonium compounds, represented by onium salts, ylides, and imides, that have long been left untouched within the frame of heteroatom chemistry mainly because of limited access. However, the recent development of methodologies for the preparation of bismuthonium compounds has enabled us to unveil their properties as well as their chemistry. The article is comprised of three sections that mainly deal with: bismuthonium salts synthesized from triphenylbismuth difluoride and organo-silanes or -stannanes
    stabilized and moderately stabilized bismuthonium ylides synthesized from triphenylbismuth(V) compounds and bismuthonium salts
    and bismuthane imides prepared by oxidative imination of bismuthanes and by reaction between triphenylbismuth(V) dihalides and sulfonamides. Synthesis, X-ray structures, and typical reaction modes of these bismuthonium compounds are delineated in the order in which they appear.

    DOI: 10.1246/bcsj.69.2673

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  • ELECTROPHILIC ALLYLATION OF ARENES WITH IN-SITU GENERATED ALLYLTRIARYLBISMUTHONIUM COMPOUND - THE BISMUTH-MEDIATED POLARITY INVERSION OF ALLYLSILANES Reviewed

    Y MATANO, M YOSHIMUNE, H SUZUKI

    TETRAHEDRON LETTERS   36 ( 41 )   7475 - 7478   1995.10

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    Reaction of triarylbismuth difluorides 1 with allyltrimethylsilane 2 in CH2Cl2 in the presence of BF3 . OEt(2) at low temperature generates allyltriarylbismuthonium compound 3 as a pale yellow solution, in which aromatic hydrocarbons and ethers, triphenylphosphine, dimethyl sulfide, p-toluenesulfinate, and thiophenol are all readily allylated to afford the corresponding allyl derivatives in moderate to good yields.

    DOI: 10.1016/0040-4039(95)01600-7

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  • SYNTHESIS, X-RAY STRUCTURE, THERMAL-STABILITY AND REACTIONS OF TRIARYL(3-OXOALKYL)BISMUTHONIUM SALTS Reviewed

    Y MATANO, N AZUMA, H SUZUKI

    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1   ( 20 )   2543 - 2549   1995.10

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    Treatment of triarylbismuth difluorides 2 with siloxycyclopropanes 3 in the presence of trimethylsilyl trifluoromethanesulfonate (triflate) or boron trifluoride-diethyl ether gave the corresponding triaryl(3-oxoalkyl)bismuthonium salts 4 as crystals, X-Ray crystallographic;analysis of the triflate 4a showed that the central bismuth atom has a distorted tetrahedral geometry with weak intramolecular coordination by the oxygen atoms of the carbonyl group and triflate anion, Whilst all onium salts 4 are thermally stable in a solid state, the triflate 4a slowly decomposed in chloroform to give triphenylbismuthane 6 and an ester 7 quantitatively, In nucleophilic solvents such as MeOH, DMSO and DMF, both triflate 4a and tetrafluoroborate 4d underwent decomposition in a complicated way to afford the bismuthane 6, 3-methoxypropanoyl compounds 8a,b, alpha,beta-unsaturated carbonyl compounds 9a,b, diphenylbismuth triflate 10a or tetrafluoroborate 10b and alkoxysulfonium salts 11a,b, The formate 12 was an additional product from 4d in DMF. The bismuthonium salt 4d reacted with dimethyl sulfide 13 and sodium benzenesulfinate 15 to afford the sulfonium salt 14 and the sulfonyl ketone 16, respectively, Reaction of the salt 4d with potassium halides 17 in DMF gave the enone 9b, formate 12 and halogeno ketone 18 in varying yields depending on the nucleophilic nature of the halogen anions employed. When treated with KOBu(t), the salt 4d underwent facile beta-elimination to yield the enone 9b. In all of these reactions, the triphenylbismuthane moiety behaved as a good leaving group.

    DOI: 10.1039/P19950002543

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  • 3-Substituted 2-Acyl-1-sulfonylaziridines from the Reaction of Triphenylbismuthonium 2-Oxoalkylides and N-Sulfonylaldimines. Reversal of the cis/trans-Isomer Ratios Depending on Base and Additive Reviewed

    Yoshihiro Matano, Masanori Yoshimune, Hitomi Suzuki

    Journal of Organic Chemistry   60 ( 14 )   4663 - 4665   1995.7

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    DOI: 10.1021/jo00119a056

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  • TRIPHENYLBISMUTHONIUM 2-OXOALKYLIDE, A MODERATELY STABILIZED BISMUTHONIUM YLIDE - GENERATION AND REACTIONS WITH SOME ELECTROPHILES Reviewed

    Y MATANO

    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1   ( 19 )   2703 - 2709   1994.10

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    Treatment of (2-oxoalkyl)triphenylbismuthonium tetrafluoroborates 3 with potassium tert-butoxide in tetrahydrofuran at -78 degrees C produced triphenylbismuthonium 2-oxoalkylides 4, which readily underwent epoxidation with the aldehydes 5 to give the alpha,beta-epoxy ketones 7 with high trans selectivity. The ylide 4a reacted with dimedone 11, the sulfonic acid 13, the thiol 15 and the isocyanate 17 to afford the corresponding ketones 12, 14, 16 and 19 in moderate to good yields. Reaction of the ylide 4c with the alpha,beta-unsaturated ketones 10 and 21 afforded the 1,2-dibenzoyl- and the 1,2,3-tribenzoyl- cyclopropanes 20 and 22, respectively, although the yields were low. In the presence of a catalytic amount of-nitrosobenzene 23, the ylide 4a suffered a unique decomposition to give the 2,2,7,7-tetramethyloct-4-ene,3,6-dione 24 in quantitative yield, while the reaction with the nitrile oxide 25 yielded the isoxazoline 26. In all of these reactions, triphenylbismuthane 6 was the additional major product.

    DOI: 10.1039/P19940002703

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  • ULTRASONIC REACTION OF TRIARYLBISMUTHINES AND TRIARYLSTIBINES WITH IODOSYLBENZENE - MILD OXIDIZING ABILITY OF THE ORGANOBISMUTH OXIDE FUNCTION FOR ORGANIC SUBSTRATES Reviewed

    H SUZUKI, T IKEGAMI, Y MATANO

    TETRAHEDRON LETTERS   35 ( 44 )   8197 - 8200   1994.10

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    Reaction of triarylbismuthines 1 with iodosylbenzene in dichloromethane under ultrasonic irradiation leads to the generation of triarylbismuthine oxides 2 as a bright yellow solution, in which activated alcohols are easily oxidized to carbonyl compounds, triphenylphosphine is converted into oxide and hydrazobenzene is rapidly dehydrogenated to azobenzene. Triphenylstibine 8 is similarly oxidized to give stibine oxide 9, which lacks the corresponding oxidizing ability.

    DOI: 10.1016/0040-4039(94)88281-9

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  • SYNTHESIS, X-RAY STRUCTURE AND REACTIONS OF (2-OXOALKYL)TRIARYLBISMUTHONIUM SALTS Reviewed

    Y MATANO, N AZUMA, H SUZUKI

    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1   ( 13 )   1739 - 1747   1994.7

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    Treatment of triarylbismuth difluorides 1 with silyl enol ethers 2 in the presence of boron trifluoride-diethyl ether or trimethylsilyl trifluoromethanesulfonate (triflate) gave (2-oxoalkyl)triarylbismuthonium tetrafluoroborates. 3 and triflates 4 in good yields. A similar reaction of the difluorides 1 with hexamethyldisiloxane in the presence of the latter acid reagent led to the formation of oxybis(triarylbismuth) ditriflates 5. X-Ray cyrstallographic analyses of compounds 3a, 4a and 5a showed that the first two onium salts have a distorted tetrahedral geometry and the last. a mu-oxo type compound, has a distorted trigonal bipyramidal geometry around the bismuth centre. The stability of these bismuthonium salts may reasonably be attributed to the intramolecular coordinative interaction between the bismuth and oxygen atoms and also low nucleophilicity of the counter ions employed. The bismuthonium salt 3f readily underwent onium exchange with the phosphine 6 and the sulfide 9 to afford the corresponding phosphonium and sulfonium salts 7 and 10. The salts 3 and 4 also underwent coupling with a variety of nucleophiles such as the enolate 11, piperidine 13, the phenoxides 15, the thiolates 17, the sulfinate 19 and the halides 21 to afford the corresponding alpha-substituted ketones 12, 14, 16, 18, 20 and 22 in moderate to good yields, together with a good recovery of triphenylbismuthine 8.

    DOI: 10.1039/P19940001739

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  • CHIRAL CHLOROBISMUTHINES STABILIZED BY THE INTRAMOLECULAR COORDINATION OF AN N,N-DIMETHYLAMINO GROUP - X-RAY STRUCTURE-ANALYSIS, ASYMMETRIC INDUCTION AT THE BISMUTH CENTER, AND DYNAMIC BEHAVIOR IN SOLUTION Reviewed

    H SUZUKI, T MURAFUJI, Y MATANO, N AZUMA

    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1   ( 23 )   2969 - 2973   1993.12

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    Chiral chlorobismuthines 3 stabilized by intramolecular coordination of an NN-dimethylamino group have been synthesized by the selective fluorodearylation of the bismuthines 1 with boron trifluoride-diethyl ether, followed by halogen exchange of the resulting fluorobismuthines 2 with brine. An X-ray crystallographic structure analysis of 3b revealed that the bismuth centre has a distorted pseudotrigonal bipyramidal structure through the formation of a hypervalent 3-centre 4-electron bond with the chlorine and nitrogen atoms at apical positions. H-1 NMR spectra of compounds 3 in CDCl3 at room temperature reflected their fixed conformation in the solid state. Chiral chlorobismuthines 7a and 7b were obtained in a similar manner starting from optically pure (R)-N,N-dimethyl-1-phenylethylamine as a mixture of two diastereoisomers (77:23 and 78:22, respectively), the isomeric ratios of which were not influenced by the equatorial aryl groups present. Variable-temperature dynamic H-1 NMR spectra of the diastereoisomeric mixture of 7a provided important information about its behaviour in solution; in [H-2(8)]toluene dynamic but reversible dissociation of intramolecular Bi-N coordination was observed only at elevated temperatures, while in [H-2(6)]-DMSO it occurred quite easily below room temperature, leading to the inversion of configuration at the chiral bismuth centre.

    DOI: 10.1039/P19930002969

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  • IMPROVED SCHMIDT SYNTHESIS OF 1,5-DISUBSTITUTED 1H-TETRAZOLES FROM KETONES Reviewed

    H SUZUKI, YS HWANG, C NAKAYA, Y MATANO

    SYNTHESIS-STUTTGART   1993 ( 12 )   1218 - 1220   1993.12

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    On treatment with an excess of sodium azide in the presence of titanium(IV) chloride in boiling acetonitrile, both aliphatic and aromatic ketones are smoothly converted to 1,5-disubstituted 1H-tetrazoles in high yields.

    DOI: 10.1055/s-1993-26027

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  • A NOVEL SYNTHESIS OF ALKYLBISMUTHONIUM SALTS AND THEIR REACTION WITH SOME NUCLEOPHILES - FIRST X-RAY STRUCTURAL-ANALYSIS OF A STABILIZED ALKYLBISMUTHONIUM TETRAFLUOROBORATE Reviewed

    Y MATANO, N AZUMA, H SUZUKI

    TETRAHEDRON LETTERS   34 ( 52 )   8457 - 8460   1993.12

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    Treatment of triarylbismuth difluorides 1 with silyl enol ethers 2 in the presence of BF3.OEt(2) gives (2-oxoalkyl)triarylbismuthonium tetrafluoroborates 3 as a stable crystalline solid, the bismuth centre of which has been found by X-ray analysis to possess a tetragonal geometry. The 2-oxoalkyl moiety of compound 3 couples with enolates and thiolates to afford the corresponding triketones 4 and alpha-thioketones 6, respectively.

    DOI: 10.1016/S0040-4039(00)61358-8

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  • UNEXPECTED FORMATION OF TRIARYLBISMUTH DIFORMATES IN THE OXIDATION OF TRIARYLBISMUTHINES WITH OZONE AT LOW-TEMPERATURES Reviewed

    H SUZUKI, T IKEGAMI, Y MATANO, N AZUMA

    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1   ( 20 )   2411 - 2415   1993.10

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    Oxidation of triphenylbismuthine 1 with ozone in toluene at -78-degrees-C gave, unexpectedly, a high yield of triphenylbismuth diformate 3, which was also obtainable as a minor product by a similar oxidation in ethyl acetate and acetone. An X-ray crystallographic study revealed that compound 3 has C2 symmetry, the geometry around the bismuth atom being best described as a distorted trigonal bipyramid as a result of strong intramolecular interaction between the bismuth and carbonyl oxygen atoms. Treatment of compound 3 with aqueous sodium acetate or halides readily converted it into the corresponding triphenylbismuth diacetate 5 or dihalides 7-9.

    DOI: 10.1039/P19930002411

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  • PHOTOCHEMICAL AZIDO LIGAND TRANSFER-REACTION OF A TRIARYLBISMUTH DIAZIDE WITH ALKYNES Reviewed

    H SUZUKI, C NAKAYA, Y MATANO

    TETRAHEDRON LETTERS   34 ( 6 )   1055 - 1056   1993.2

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    Irradiation of a triarylbismuth diazide in benzene in the presence of alkynes results in the transfer of one of the azido ligands to the triple bond, leading to N-unsubstituted 1,2,3-triazoles in fair to moderate yields.

    DOI: 10.1016/S0040-4039(00)77490-9

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  • Synthesis and Reactions of Some Crowded Triorganobismuthines Reviewed

    Yoshihiro Matano, Masamichi Kinoshita, Hitomi Suzuki

    Bulletin of the Chemical Society of Japan   65 ( 12 )   3504 - 3506   1992

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    Bismuth trichloride reacts smoothly with mesityl- and 2,4,6-triisopropylphenylmagnesium bromides in boiling tetrahydrofuran to form the corresponding triarylbismuthines in good yields, while a similar reaction with 2,4,6-triisopropylphenylmagnesium bromide halts at diarylation stage, giving chlorobis(2,4,6-triisopropylphenyl)bismuthine as the sole product. Several crowded alkyl-, alkenyl-, and alkyn-yldiarylbismuthines have been prepared from the above diarychlorobismuthine through the reaction with an appropriate organolithium reagent.

    DOI: 10.1246/bcsj.65.3504

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  • N-Tosyltriarylbismuthimines. Synthesis and Reactions with Some Electrophiles Reviewed

    Hitomi Suzuki, Chie Nakaya, Yoshihiro Matano, Takuji Ogawa

    Chemistry Letters   20 ( 1 )   105 - 108   1991

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    DOI: 10.1246/cl.1991.105

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  • Product‐determining factors in the grignard reactions of benzophenones. The role of the structure of alkyl groups in grignard reagents Reviewed

    Kazuhiro Maruyama, Yoshihiro Matano, Toshimasa Katagiri

    Journal of Physical Organic Chemistry   4 ( 8 )   501 - 515   1991

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    The mechanism of the Grignard reactions of substituted benzophenones with two kinds of alkyl Grignard reagent, n‐C3H7MgBr, and i‐C3H7MgBr, was investigated. In these reactions, both addition and reduction products were also generated. Based on the results of product analysis and stopped‐flow, ESR and association measurements, it was confirmed that the product distribution was governed by several factors: the oxidizing ability of benzophenones, the association ability of Grignard reagents and the structure of alkyl groups of Grignard reagents. In particular, the strength of CMg and β‐CH bonds of Grignard reagents could strongly affect the product distribution. Copyright © 1991 John Wiley &amp
    Sons Ltd.

    DOI: 10.1002/poc.610040806

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  • Photochemically induced single electron transfer reactions of benzils with allylstannane. Direct observation of reactive intermediates by ESR method Reviewed

    Kazuhiro Maruyama, Yoshihiro Matano

    Bulletin of the Chemical Society of Japan   63 ( 8 )   2218 - 2223   1990.8

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    Although the photochemically induced reaction of benzil with allyltrimethylstannane in benzene afforded α-allylbenzoin as a major product, benzil did not react thermally with the same reagent. An ESR observation disclosed that the benzil anion radical ion-paired upon contact with trimethylstannyl cation (BSnMe3) was generated during irradiation. Its structure was confirmed by the detection of satellite signals arising from tin isotopes. Moreover, a triplet radical pair was also observed during the photolysis of a solid solution containing benzil and allylstannane at 77 K. This reaction proceeded via a single electron transfer from allylstannane to photoexcited benzil, followed by a cleavage of the C-Sn bond of the allyltin cation radical. Ultimately, a radical pair composed of BSnMe3 and the allyl radical was formed and their coupling gave α-allylbenzoin as an isolated product.

    DOI: 10.1246/bcsj.63.2218

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  • Non-catalyzed Thermal Reactions of Acylquinones with Allylstannanes Reviewed

    Kazuhiro Maruyama, Yoshihiro Matano

    Bulletin of the Chemical Society of Japan   62 ( 12 )   3877 - 3885   1989

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    Thermal reactions of acylquinones with allylstannanes in benzene afforded several kinds of product after column chromatography on silica gel; acyl allyl quinones, acyl allyl epoxy quinones, cyclopentanoid compounds including stannyl moiety, allyl hydroxy quinones, acyl hydroquinones, and acyl allyl hydroquinones. The main product comprises cyclopentanoid compounds, which are novel [2+3] cyclo adducts with 1,2-migration of trialkylstannyl moiety. Spectroscopic examinations (<SUP>1</SUP>H NMR and Vis-UV) enabled us to confirm the reaction pathways that four types of precursors were initially generated via polarized tight pair and inverted to isolated products during purification by column chromatography. Similar reactions in acetonitrile showed a remarkable difference in the reactivity, that is, acyl allyl quinones and the corresponding hydroquinones are obtained, but the [2+3] cyclo adducts are not produced at all. From <SUP>1</SUP>H NMR examination, it was confirmed that three types of precursor are generated via solvent separated ion pairs at the initial stage. The rather strong reactivity of acylquinones towards allylstannanes will be due to electron withdrawing ability of acyl group.

    DOI: 10.1246/bcsj.62.3877

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  • Application of Electron Spin Resonance Spectroscopy to Reactions of p-Quinones and 9,10-Phenanthraquinone with Allylstannanes Reviewed

    Kazuhiro Maruyama, Yoshihiro Matano

    NIPPON KAGAKU KAISHI   1989 ( 8 )   1351 - 1357   1989

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    Allylstannanes recently attract much interest in the field of organic synthesis and photochemistry because of their remarked reactivities toward electrophiles. In the photochemical reactions of some electron acceptable substrates with allylstannanes, photo-induced single electron transfer mechanism has been proposed mainly based on the product analyses. However, few attempts to clarify the mechanism by detecting directly the reactive intermediates have been made so far. We have applied ESR technique to the photochemical and thermal reactions of quinones with allylstannanes. During irradiation, semiquinone radical combined with trialkylstannyl moiety and allyl radical were observed simultaneously in the case of p-quinones. No radical was detected in the dark. On the other hand, in the case of 9,10-phenanthraquinone, intense signal of semiquinone radical coordinated with trialkylstannyl moiety was observed not only during irradiation but also in the dark. It is doubtless, in the latter case, that ability of the two neighboring carbonyi oxygens to coordinate stannyl moiety is the most important factor for inducing the thermal electron transfer. The results obtained by ESR disclosed us the features of reactive paramagnetic intermediates and enabled us to make sure the mechanism of these allylations, 1) photo-induced or thermal single electron transfer occurred from allylstannane to quinone. 2) Cleavage of the cation radical by assist of the quinone anion radical generated radical pair. 3) Combination between semi-quinone radical combined with stannyl moiety and allyl radical afforded allylated products. Evidently, regioselectivity of allylation was dependent on the spin densities of radical intermediates. © 1989, The Chemical Society of Japan. All rights reserved.

    DOI: 10.1246/nikkashi.1989.1351

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Books

  • Main Group Strategies towards Functional Organic Materials

    Yoshihiro Matano( Role: Sole author ,  Phosphorus-based Porphyrins)

    Wiley  2018.3  ( ISBN:9781119235972

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    Total pages:560   Responsible for pages:265–294   Language:English Book type:Scholarly book

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  • Organic Redox Systems: Synthesis, Properties, and Applications

    Yoshihiro Matano( Role: Sole author ,  Phospholes and Related Compounds: Syntheses, Redox Properties, and Applications to Organic Electronic Devices)

    Wiley  2015.12  ( ISBN:9781118858745

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    Total pages:616   Responsible for pages:477–502   Language:English Book type:Scholarly book

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  • Topics in Current Chemistry: Bismuth-Mediated Organic Reactions

    Yoshihiro Matano( Role: Sole author ,  Pentavalent Organobismuth Reagents in Organic Synthesis: Alkylation, Alcohol Oxidation, and Cationic Photopolymerization)

    Springer  2012.1  ( ISBN:9783642272387

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    Total pages:278   Responsible for pages:19–44   Language:English Book type:Scholarly book

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  • Comprehensive Organometallic Chemistry III

    Yoshihiro Matano( Role: Sole author ,  Antimony and Bismuth)

    Elsevier  2006.12  ( ISBN:9780080445991

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    Total pages:786   Responsible for pages:425–456   Language:English Book type:Scholarly book

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  • Main Group Metals in Organic Synthesis

    Yoshihiro Matano( Role: Sole author ,  Antimony and Bismuth in Organic Synthesis)

    Wiley-VCH  2004.4  ( ISBN:9783527305087

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    Total pages:905   Responsible for pages:753–811   Language:English Book type:Scholarly book

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  • Organobismuth Chemistry

    Yoshihiro Matano, Tohru Ikegami( Role: Joint author)

    Elsevier  2001.2 

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    Total pages:636   Responsible for pages:21–245   Language:English Book type:Scholarly book

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  • Organobismuth Chemistry

    Yoshihiro Matano, Tohru Ikegami( Role: Joint author)

    Elsevier  2001.2 

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    Total pages:636   Responsible for pages:247–327   Language:English Book type:Scholarly book

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  • 芳香環C–H結合直接アミノ化の最前線-異なるアプローチによる¬C–N結合の形成

    俣野善博( Role: Sole author ,  pp. 70-71)

    化学同人  2018.9 

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  • Chemical Science of π-Electron Systems

    Yoshihiro Matano( Role: Sole author ,  Heteroatom-Modified Porphyrinoids)

    Springer  2015.11  ( ISBN:9784431553571

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    Total pages:777   Responsible for pages:223–241   Language:English Book type:Scholarly book

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  • 高次π空間の創発と機能開発

    俣野 善博( Role: Sole author ,  ヘテロ元素を含む新奇ポルフィリンπ空間の創発と機能化)

    シーエムシー  2013.3  ( ISBN:9784781307589

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    Total pages:245   Responsible for pages:123–127   Language:Japanese Book type:Scholarly book

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  • 有機金属化学の最前線(現代化学増刊44)

    俣野 善博( Role: Sole author ,  14〜16族高周期典型元素化合物の機能)

    東京化学同人  2011.3  ( ISBN:9784807913442

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    Total pages:238   Responsible for pages:102–114   Language:Japanese Book type:Scholarly book

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  • 実験化学講座第5版

    今堀 博, 俣野 善博( Role: Joint author ,  人工光合成)

    丸善  2005.7  ( ISBN:9784621073278

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    Total pages:409   Responsible for pages:114–131   Language:Japanese Book type:Scholarly book

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  • 実験化学講座第5版

    俣野 善博( Role: Sole author ,  銀化合物による酸化)

    丸善  2004.7  ( ISBN:9784621073162

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    Total pages:462   Responsible for pages:120–127   Language:Japanese Book type:Scholarly book

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  • 実験化学講座第5版

    俣野 善博( Role: Sole author ,  ビスマス化合物による酸化)

    丸善  2004.7  ( ISBN:9784621073162

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    Total pages:462   Responsible for pages:173–176   Language:Japanese Book type:Scholarly book

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  • 実験化学講座第5版

    俣野 善博( Role: Sole author ,  タリウム化合物による酸化)

    丸善  2004.7  ( ISBN:9784621073162

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    Total pages:462   Responsible for pages:127–135   Language:Japanese Book type:Scholarly book

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  • 実験化学講座第5版

    俣野 善博( Role: Sole author ,  水銀化合物による酸化)

    丸善  2004.7  ( ISBN:9784621073162

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    Total pages:462   Responsible for pages:113–120   Language:Japanese Book type:Scholarly book

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  • 実験化学講座第5版

    俣野 善博( Role: Sole author ,  鉛化合物による酸化)

    丸善  2004.7  ( ISBN:9784621073162

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    Total pages:462   Responsible for pages:103–113   Language:Japanese Book type:Scholarly book

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  • 実験化学講座第5版

    俣野 善博( Role: Sole author ,  ケトン:アシル化、カルボニル化による合成)

    丸善  2003.11  ( ISBN:4621073141

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    Responsible for pages:244–294   Language:Japanese Book type:Scholarly book

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  • 有機金属反応剤ハンドブック

    俣野 善博( Role: Sole author ,  ビスマス)

    化学同人  2003.6  ( ISBN:9784759809367

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    Total pages:272   Responsible for pages:246–250   Language:Japanese Book type:Scholarly book

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  • 季刊化学総説No. 34「有機超原子価化合物」

    俣野善博, 鈴木仁美( Role: Joint author)

    学会出版センター  1998.4  ( ISBN:9784762218804

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    Total pages:272   Responsible for pages:149–165   Language:Japanese Book type:Scholarly book

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  • Chemistry of Arsenic, Antimony and Bismuth

    Hitomi Suzuki, Yoshihiro Matano( Role: Joint author)

    Blackie Academic and Professional  1998 

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    Responsible for pages:283–343   Language:English Book type:Scholarly book

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MISC

  • Bismuth in organic transformations

    H Suzuki, T Ikegami, Y Matano

    SYNTHESIS-STUTTGART   ( 3 )   249 - 267   1997.3

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    Language:English   Publishing type:Book review, literature introduction, etc.   Publisher:GEORG THIEME VERLAG  

    This review presents a systematic and comprehensive survey of various applications of bismuth compounds to organic transformations. The review is organized on the basis of the type of compounds, and within each type reactions are organized on the basis of the transformations involved. Emphasis is placed on the recent literature, and on those reactions which the authors feel have synthetic potential. Less common aspects of organobismuth compounds are also included briefly.

    DOI: 10.1055/s-1997-1194

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  • ジアザポルフィリン二量体の磁気特性

    丸山裕久, 大桃理志, 川俣昌弘, 古川貢, 俣野善博

    電子スピンサイエンス学会年会講演要旨集   55th   2016

  • Synthesis and photochemistry of diazaporphyrin derivatives

    46 ( 1 )   29 - 36   2015.4

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  • Synthesis and functionalization of π-conjugated phosphole oligomers and polymers by utilizing characteristic properties of acetylene units

    1 - 5   2011

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  • Synthesis, Structure and Reactivity of Monophosphaporphyrin

    Nakashima Makoto, Nakabuchi Takashi, Matano Yoshihiro, Umeyama Tomokazu, Imahori Hiroshi

    Abstracts of Symposium on Physical Organic Chemistry   37 ( 0 )   61 - 61   2007

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    Language:Japanese   Publisher:The Society of Physical Organic Chemistry, Japan  

    The first 21-phosphaporphyrin (1) and its pi-expanded analog (2) were prepared via [3+1] type acid-promoted condensation of phosphatripyrrane with a pyrrole derivative. When [Rh(CO)&lt;SUB&gt;2&lt;/SUB&gt;Cl]&lt;SUB&gt;2&lt;/SUB&gt; was added after the DDQ oxidation, the rhodium(III)-porphyrin (3) was isolated. &lt;SUP&gt;1&lt;/SUP&gt;H NMR spectra of the 18pi-monophosphaporphyrins 1 and 3 suggested that the phosphaporphyrins possess high aromaticity in terms of magnetic criterion. On the other hand, the 22pi-phosphaporphyrin 2 showed a smaller ring current effect in the &lt;SUP&gt;1&lt;/SUP&gt;H NMR spectrum. In the UV-Vis absorption spectra, the Soret- and Q-type bands of 1 were red-shifted as compared to those of TPP. The observed electrochemical redox potentials of 1 and 2 clearly indicate that the HOMO-LUMO energy gaps are considerably smaller than that of TPP. In the crystal structures of 1, 2, and 3, the porphyrin rings of 1 and 2 are slightly ruffled, whereas that of 3 is significantly distorted.

    DOI: 10.11494/kisoyuki.37.0.61.0

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  • Synthesis and Properties of Phosphaporphyrin

    Nakabuchi Takashi, Nakashima Makoto, Miyajima Tooru, Matano Yoshihiro, Umeyama Tomokazu, Imahori Hiroshi

    Abstracts of Symposium on Physical Organic Chemistry   18 ( 0 )   17 - 17   2006

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    Language:Japanese   Publisher:The Society of Physical Organic Chemistry, Japan  

    Core-modified porphyrins are one of the porphyrin analogues, in which at least one core nitrogen atom is replaced by another atom. Although the chemistry of core-modified porphyrins has attracted much attention, phosphorous-containing porphyrins, namely &quot;phosphaporphyrins&quot;, have not been prepared. Here we report the first synthesis of phosphaporphyrin and its aromaticity as well as optical and electrochemical properties. A phosphaporphyrin was synthesized via acid-promoted condensation of phosphatripyrrane with 2,5-bis[hydroxy(phenyl)methyl]thiophene. The NMR and UV-vis absorption spectra, and CV has revealed that the phosphaporphyrin possesses a considerable aromaticity and a relatively narrow HOMO-LUMO energy gap.

    DOI: 10.11494/kisoyuki.18.0.17.0

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  • 有機太陽電池の分子設計 (環境技術特集 有機太陽電池の変換効率の高度化と固体化技術) -- (色素増感太陽電池の固体化技術)

    今堀 博, 俣野 善博, 森 幸恵

    マテリアルステージ   2 ( 9 )   43 - 48   2002.12

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    Language:Japanese   Publisher:技術情報協会  

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Research Projects

  • 含窒素ポルフィリンの基礎学理の構築および機能性色素としての展開

    Grant number:22H02061

    2022.4 - 2026.3

    System name:科学研究費助成事業

    Research category:基盤研究(B)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\17160000 ( Direct Cost: \13200000 、 Indirect Cost:\3960000 )

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  • アザポルフィリンラジカルをプラットフォームとする高密度共役系の構築

    Grant number:21H05476

    2021.9 - 2023.3

    System name:科学研究費助成事業

    Research category:学術変革領域研究(A)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\7800000 ( Direct Cost: \6000000 、 Indirect Cost:\1800000 )

    本研究の目的は、meso窒素上に置換基を持つ5-モノアザポルフィリン(RMAP)と5,15-ジアザポルフィリン(RDAP)のラジカルを合成する簡便な方法を確立し、得られた誘導体の構造―物性相関を明らかにした上で、高密度共役の実現へ向け、これらのラジカルをプラットフォームとして利用することである。2021年度は、主に以下の二つの課題に取り組んだ。
    課題1.RMAP金属錯体の合成:アザテトラピリンの鋳型環化法を用いて、カチオン性RMAP亜鉛錯体を合成することに成功した。得られた錯体について、NMR、紫外/可視/近赤外吸収スペクトル、CV測定を行い、芳香族性、光物性、電気化学特性を調べ、対応するカチオン性RDAP亜鉛錯体と比較した結果、分子の対称性と電荷の影響がアザポルフィリン環の環電流効果や酸化還元特性に顕著に現れることが明らかとなった。また、鋳型環化を経由しないRMAPの新規合成法を開発することに成功した。
    課題2.新規RDAPラジカルの合成:共有結合や配位結合を介してRDAPラジカルを連結することを目的として、RDAPを含むフェニレン架橋型ポルフィリン三量体の合成を行った。具体的には、ポルフィリンを置換基とするジブロモジピリンの鋳型環化反応を利用して目的物を合成し、NMR、ESR、紫外/可視/近赤外吸収スペクトル、CV測定を用いて得られた三量体の物性を調べ、参照系となる単量体の物性と比較した。その結果、両側のポルフィリン環が中心に位置するRDAPラジカルの磁気特性や光物性に与える影響は極めて小さいことが明らかとなった。
    得られた研究成果について、国際会議での依頼講演を含む5つの学会発表を行ったほか、2報の論文として報告した。

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  • Development and functionalization of NIR-light-responsive diazaporphyrin sensitizers

    Grant number:18H01961

    2018.4 - 2022.3

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for Scientific Research (B)

    Awarding organization:Japan Society for the Promotion of Science

    Matano Yoshihiro

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    Grant amount:\17290000 ( Direct Cost: \13300000 、 Indirect Cost:\3990000 )

    In this research project, we have investigated several subjects concerning the chemistry of azaporphyrins where meso carbons are partially replaced with nitrogen atoms. First, we established several convenient methods for the synthesis of several types of azaporphyrin derivatives. Second, we revealed the aromaticity, optical and electrochemical properties, and singlet-oxygen-generating ability of a series of novel azaporphyrins obtained. Finally, we constructed near-infrared-light-responsive azaporphyrin-based sensitizers and shed light on their potential as functional dyes used for medical application such as photodynamic therapy.

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  • Development of heteroarene-fused and pi-expanded diazaporphyrins as n-type semiconductors

    Grant number:15K13762

    2015.4 - 2018.3

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for Challenging Exploratory Research

    Awarding organization:Japan Society for the Promotion of Science

    MATANO YOSHIHIRO, IMAHORI Hiroshi, NAKANO Haruyuki

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    Grant amount:\4030000 ( Direct Cost: \3100000 、 Indirect Cost:\930000 )

    In order to develop the chemistry of diazaporphyrins that have high electron-accepting and light-harvesting properties, we have (i) synthesized new diazaporphyrin derivatives bearing various substituents at the periphery, (ii) disclosed their structure-property relationships, and (iii) applied some derivatives in organic solar cells. As a result, we have found that the amino-substituted donor-acceptor-type diazaporphyrins show the intramolecular charge-transfer character derived from the intrinsically electron-withdrawing nature of the diazaporphyrin. Furthermore, we have succeeded in fabricating dye-sensitized solar cells using some diazaporphyrin-based dyes and revealed their potential as the photofunctional materials.

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  • 近赤外光感応性をもつジアザポルフィリンーポルフィリン連結分子の創製と利用

    Grant number:15H00931

    2015.4 - 2017.3

    System name:科学研究費助成事業

    Research category:新学術領域研究(研究領域提案型)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\6240000 ( Direct Cost: \4800000 、 Indirect Cost:\1440000 )

    本研究の目的は、ジアザポルフィリン-ポルフィリン連結分子およびその関連化合物の合成法を確立し、異なるπ系の連結が生み出す物性面での相乗効果を明らかにした上で、近赤外光感応性を持つ医療用増感剤として利用するための道標をつけることである。本年度は、主に次の三つの課題に取り組んだ。(i)非対称置換されたπ共役ジアザポルフィリン誘導体の合成、(ii) (i)で得られたジアザポルフィリン誘導体の光物性、電気化学特性、および一重項酸素発生効率の解明、(iii) ジアザポルフィリン誘導体を用いた色素増感太陽電池の作製とデバイス特性の評価。まず、ジアザポルフィリン環β位の位置選択的な臭素化により得られるブロモ体を共通の出発原料として、鈴木―宮浦カップリング反応により、電子供与性置換基とカルボキシフェニル基で非対称に置換されたDonor-Acceptor型ジアザポルフィリンを系統的に合成した。また、得られた化合物のNMRスペクトル・吸収スペクトル・酸化還元電位・蛍光量子収率の測定およびDFT計算により、π系全体の構造、吸収特性、発光特性、および電気化学特性を調べた。その結果、ジアザポルフィリン環へのアミノ基の導入により大きな電荷移動特性が発現し、吸収帯の大幅な長波長化を達成できることが明らかとなった。次いで、高い光捕集能をもつジアザポルフィリン誘導体を増感剤とする色素増感太陽電池を作製し、デバイス特性を評価した。その結果、複数の電子供与性置換基の導入により光電変換効率が大幅に向上することが明らかとなった。さらに、医療用色素への展開を念頭に置き、一部の化合物について一重項酸素発生効率を評価し、水溶性を持つジアザポルフィリン誘導体を新たに合成した。

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  • 高い近赤外光感応性をもつ水溶性ジアザポルフィリン増感剤の開発

    Grant number:25109524

    2013.4 - 2016.3

    System name:科学研究費助成事業

    Research category:新学術領域研究(研究領域提案型)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\7280000 ( Direct Cost: \5600000 、 Indirect Cost:\1680000 )

    本年度は、近赤外光に対して高い感応性を持つジアザポルフィリン増感剤の開発を見据えて、期間内に主に次の三つの課題に取り組んだ。(i) 外周部にπ共役可能な置換基を持つジアザポルフィリンの合成、(ii) 水溶性ジアザポルフィリンの合成、(iii)課題(i)で合成した色素の光物性および電気化学特性に対する外周部置換基効果の解明。まず、β-ブロモジアザポルフィリンニッケル錯体および亜鉛錯体のクロスカップリング反応を利用して、ジアザポルフィリンの外周部にπ共役が可能な置換基を導入した。次いで、得られた化合物のX線結晶構造解析、NMRスペクトル・吸収スペクトル・発光スペクトル・酸化還元電位の測定により、π系の構造、吸収・発光特性、および、電気化学特性を調べた。その結果、分子内電荷移動特性の発現により吸収・発光帯の大幅な長波長化が達成できることや、π共役の拡張により電子スピンの非局在化が効率よく起こることが明らかとなった。一部の誘導体については、電荷移動型の吸収帯が800nmを超える近赤外領域に達することを見出した。さらに、外周部の置換基としてカルボキシフェニル基を持つジアザポルフィリン誘導体を合成し、その水溶性を調べた。その結果、弱塩基性で水溶性を示すことを確認した。得られた知見は、可視光のみならず近赤外光に対して高い感応性を持つ医療用増感剤や太陽電池用増感剤を開発するうえで、ジアザポルフィリンが有力な母核となることを示している。

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  • Construction of Phosphole-Containing Hybrid pi-Conjugated Molecules and Their Application to Organic Devices

    Grant number:25288020

    2013.4 - 2016.3

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for Scientific Research (B)

    Awarding organization:Japan Society for the Promotion of Science

    Matano Yoshihiro, NAKANO Haruyuki, KIMURA Yoshifumi

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    Grant amount:\18850000 ( Direct Cost: \14500000 、 Indirect Cost:\4350000 )

    New efficient methods for the synthesis of phosphole/thiophene-containing π-conjugated molecules were established, and their structure-property relationships were unveiled using various spectroscopic techniques and X-ray diffraction analyses. Some derivatives with high visible-light absorbing ability were used for organic solar cells. In addition, a new class of highly fluorescent derivatives was constructed. All the results show that the newly constructed phosphole/thiophene-containing hybrid derivatives would be promising candidates as organic materials.

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  • Creation of core-modified azaporphyrins and their application to organic solar cells

    Grant number:25620149

    2013.4 - 2015.3

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for Challenging Exploratory Research

    Awarding organization:Japan Society for the Promotion of Science

    MATANO Yoshihiro, NAKANO Haruyuki

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    Grant amount:\4160000 ( Direct Cost: \3200000 、 Indirect Cost:\960000 )

    In this research project, we aimed to create new core-modified azaporphyrins that absorb visible-near infrared (NIR) light for application to organic solar cells. First, we established a general method for introducing π-conjugative substituents onto the peripheral carbons of diazaporphyrins. We investigated the optical and electrochemical properties of the newly prepared diazaporphyrins. The introduction of an electron-donating substituent to the peripheral carbon causes a large enhancement of the visible-light harvesting ability of the diazaporphyrin π-system. Second, we synthesized novel dipyrrin-boron and azadipyrrin-boron complexes bearing π-conjugative substituents on the pyrrole rings. We have revealed that the aza-substitution of π-extended dipyrrin-boron complexes is an efficient method for enhancing the NIR light-harvesting ability.

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  • 典型元素を含む新奇ポルフィリンπ空間の機能化と集積化

    Grant number:23108708

    2011.4 - 2013.3

    System name:科学研究費助成事業

    Research category:新学術領域研究(研究領域提案型)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\4550000 ( Direct Cost: \3500000 、 Indirect Cost:\1050000 )

    本年度では『典型元素の特性が最大限に発揮されるようなπ空間を創発し、その機能を利用する』ことを目的として、期間内に主に次の課題に取り組んだ。(i)メソ位に窒素を含むジアザポルフィリンの合成と、それらの構造・物性・配位挙動の解明。(ii)π系が高度に拡張されたジアザポルフィリン二量体の合成、(iii)ジアザポルフィリンの特性を活かした有機太陽電池の作製と性能評価。まず、アジ化ナトリウムとジブロモジピリンとの反応を利用して、β無置換ジアザポルフィリンフリーベースを20%程度の単離収率で合成する事に成功した。次いで、得られてフリーベースの錯形成により、各種金属錯体を構築し、その吸収特性、発光特性、および電子受容性・電子供与性を調べた。その結果、ジアザポルフィリンπ系の物性が、ポルフィリンの場合と同様、中心金属の種類に大きく依存することが明らかとなった。さらに、β無置換ジアザポルフィリン-ニッケル錯体のβ位を位置選択的に臭素化した後、パラジウム触媒を用いて反応させることにより、ジアザポルフィリン二量体を合成する事に成功した。各種スペクトル測定および理論計算の結果、この二量体は高い平面性を持ち、π系は大きく拡張されていることを見いだしている。また、一部の誘導体についてはその吸収帯が近赤外領域に達することから、色素増感太陽電池への利用も検討している。以上の結果は、アザポルフィリン誘導体の構造―物性相関を理解する上で重要な知見を与えるものである。

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  • Construction and Search for the Function of Novel Phosphole-Based π-Conjugated Molecules

    Grant number:22350016

    2010 - 2012

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for Scientific Research (B)

    Awarding organization:Japan Society for the Promotion of Science

    MATANO Yoshihiro

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    Grant amount:\20020000 ( Direct Cost: \15400000 、 Indirect Cost:\4620000 )

    New efficient methodsfor the synthesis of phosphole-containing π-conjugated molecules were established, and their structure-property relationships were unveiled by various spectroscopy and X-ray crystallography. In addition, some derivatives with high electron-transporting and/or visible-light absorbing abilities were utilized for organic photovoltaics. All the results represent high potential of the newly constructed phosphole derivatives as functional organic materials.

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  • 15族元素を含む新奇核置換ポルフィリンπ空間の創発と機能化

    Grant number:21108511

    2009 - 2010

    System name:科学研究費助成事業

    Research category:新学術領域研究(研究領域提案型)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\4680000 ( Direct Cost: \3600000 、 Indirect Cost:\1080000 )

    リンや硫黄などの典型元素とポルフィリンの融合により新奇なπ空間を構築し、基礎物性の解明および光・電子材料としての利用を目指して研究を進めてきたが、平成22年度は以下の課題に取り組んだ。(1)拡張π平面を持つ金属架橋ポルフィリン二量体の光物性と電気化学特性に対する金属架橋効果の解明、(2)湾曲したπ系を持つメソ置換カリックスフィリンの合成、および(3)ホスホールを含む核置換ポルフィリンの参照化合物(鎖状π系)の合成と物性評価。(1)メソ-ホスフィノポルフィリンと2価のパラジウム塩あるいは白金塩との反応により得られる金属架橋ポルフィリン二量体は、高いπ平面性を持ち、金属-π結合に由来する特異な吸収特性を示すが、架橋金属が二量体の光物性や電気化学特性に与える影響については、十分に解釈できていなかった。そこで、金属架橋ポルフィリン二量体および参照化合物の光ダイナミクス、酸化還元挙動、MCDスペクトルの測定を行い、架橋金属が諸物性に与える影響を明らかにした。(2)歪んだポルフィリン系π空間を集積化する新しい方法論を提案する目的で、メソ位にリン原子を組み込んだメソ置換カリックスフィリン(5-ホスファフロリン)を新たに設計し、ジチエニルホスフィンあるいはジフリルホスフィン誘導体とジピロメタンとの脱水縮合反応を利用して合成した。得られた化合物の一部に関してはX線結晶構造解析に成功し、リン架橋により環状π系が湾曲した構造をとり、リン上の非共有電子対は環外へ配向することを明らかにした。(3)ホスホールのα位にπ共役官能基を導入する効率的な合成法を確立し、ポルフィリンの参照系となる種々の鎖状π共役ホスホールを構築し、その構造-物性相関を明らかにした。

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  • ポルフィリン類縁体のハイブリッド化による多機能型環状配位子の開発

    Grant number:20036028

    2008 - 2009

    System name:科学研究費助成事業

    Research category:特定領域研究

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\3800000 ( Direct Cost: \3800000 )

    ポルフィリン、カリックスピロール、およびそれらが融合した化合物であるカリックスフィリンにピロール以外の複素環を組み込むことで、多彩な配位形態の発現が可能な新しいタイプの大環状多座配位子を構築することができる。我々は、R,X,N_2型・S,X,N_2型の大環状配位子(X=N,S)の開発と利用をめざして、ホスホールやチオフェンを含むハイブリッドポルフィリン類縁体の化学に関する研究を行っている。今年度は、まず、5,10-ポルフォジメテン型R,S,N_2カリックスフィリンに焦点を絞り、その配位特性の詳細を明らかにした。具体的には、X線結晶構造解析・各種スペクトル測定により、R,S,N_2カリックスフィリンが中性のP,N二座配位子としてロジウム中心に配位すること、および、得られた錯体においてR,S,N_2カリックスフィリンがhemilabileな配位子として振る舞うことなどを見いだした。次いでホスホールと含窒素複素環からなる新しい鎖状P,N配位子の合成と錯形成について検討し、得られたπ共役化合物の構造-物性相関を明らかにした。具体的には、α-エチニルボスホールのHuisgen反応を利用したホスホール=トリアゾールπ共役分子の簡便かつ系統的な合成法を確立し、パラジウムや白金に対する錯形成能を調べた。その結果、パラジウム錯体において、ボスホール=トリアゾール分子はP,N二座配位子として振る舞い、配位によるπ系の大きな歪みや金属-配位子間のCT相互作用が吸収スペクトルのブロード化を引き起こすことを見いだした。

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  • 第三周期典型元素を含む核置換ポルフィリンの構造と物性に関する研究

    Grant number:20038039

    2008 - 2009

    System name:科学研究費助成事業

    Research category:特定領域研究

    Awarding organization:日本学術振興会

    中野 晴之, 俣野 善博

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    Grant amount:\3200000 ( Direct Cost: \3200000 )

    本研究は、理論家と実験家が協力し、第三周期典型元素を含む核置換ポルフィリンの化学を分子理論という立場から体系化し、新規化学事象の解明を行うことを目的としている。本年度は、コアのリン原子がオキソ化されたポルフィリンおよびホスファポルフィリンから得られた金属錯体の芳香族性に関して実験・理論両面から検討を加え、参照化合物との比較から芳香族性・反芳香族性を定量的に評価した。
    1. コアのリン原子がオキソ化されたホスファポルフィリンの芳香族性については、P, S, N_2型18πホスファポルフィリンと過酸化水素との反応により得られる20πポルフィリン(イソフロリン)の芳香族性を、NMRで観測される環電流効果、および、密度汎関数により計算されるNICS値により評価した。その結果、P, S, N_2型18πホスファポルフィリンは高い芳香族性を有すること、一方、20πポルフィリンは予想に反して弱い反芳香族性を有することがわかった。弱い反芳香族性の原因には、大きく歪んだ、堅固なπ系が考えられる。
    2. ホスファポルフィリン金属錯体の芳香族性については、18πホスファポルフィリンの錯形成により得られる18πロジウムポルフィリンおよび20πパラジウムイソフロリンの芳香族性を、同様の手法により評価した。これらの錯体では金属中心の配位形態に合わせてπ平面が柔軟に歪むため、18πロジウムポルフィリンの芳香族性は対応するフリーベース体の芳香族性に比べてやや小さくなり、20πパラジウムイソフロリンは、20π系を持つにもかかわらず、弱い反芳香族性しか示さなかった。ただし、中心金属としてマグネシウムを導入すると20πポルフィリン錯体の反芳香族性が向上するという結果も得ており、錯体のパラメータ(π系の電子状態、中心金属の酸化数や配位数など)が核置換ポルフィリンの芳香族性に与える影響を系統的に解明するための基礎的知見を得た。

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  • ホスホール環を含むハイブリッドカリックスフィリン錯体の合成と利用

    Grant number:19027030

    2007

    System name:科学研究費助成事業

    Research category:特定領域研究

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\2400000 ( Direct Cost: \2400000 )

    カリックスアレーンとポルフィリンが融合した化合物であるカリックスフィリンは、柔軟な骨格と酸化還元活性なπ共役平面を併せ持つ新しいタイプの大環状多座配位子である。しかしながら、カリックスフィリン金属錯体の触媒活性に関しては全く報告例がなかった。本研究では、ホスホール、ピロール、および他の複素環が組み込まれたさまざまなハイブリッドカリックスフィリン配位子を構築し、複数の典型元素が織りなす協同効果がうまく発現されるような反応性金属触媒を創製することを目標として研究を進めてきた。まず、ホスファトリピランとピロール、フラン、およびチオフェン誘導体との酸触媒縮合環化反応と引き続く酸化反応により、14πおよび16πP,N2,X型カリックスフィリンを合成し、X線結晶構造解析によりその構造を明らかにした。次いで、パラジウム、ロジウム、および金との錯形成反応を行い、得られた錯体の構造とπ系の電子状態を調べた。ここで、0価パラジウムと16πP,N2,Sハイブリッドとの組み合わせでは、金属と配位子の間で酸化還元が起こり、2価のパラジウム錯体(Pd-P, N2, X錯体)が生成するという興味深い知見を得た。さらに、パラジウム錯体とロジウム錯体を用いて、Heck反応とアセチレンのヒドロシリル化反応をそれぞれ検討し、これらの錯体が触媒として振る舞うことや、カリックスフィリン骨格を構成する複素環の組み合わせにより触媒活性ならびに反応の選択性が大きな影響を受けることを明らかにした。

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  • Development of Highly Efficient Oxidation Reaction and Polymerizaztionby Utilizing the Oxidizing Ability of HyPERvalent Bismuth

    Grant number:17350018

    2005 - 2007

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for Scientific Research (B)

    Awarding organization:Japan Society for the Promotion of Science

    MATANO Yoshihiro

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    Grant amount:\16090000 ( Direct Cost: \15100000 、 Indirect Cost:\990000 )

    We have investigated three main topics to develop new reactions (oxidations and photo-induced cationic polymerizations) by utilizing the characteristic properties of the pentavalent bismuth. Firstly, various tetraarylbismuthonium salts were prepared and used as oxidants for alcohol oxidation. Primary and secondary alcohols were efficiently converted to the corresponding carbonyl compounds by treatment with the above Bi(V) oxidants in the presence of an organic base. It has been found that the introduction of ortho-substituents and/or electron-withdrawing para-substituents onto the aryl ligands enhances the oxidizing ability of the bismuthonium salts significantly. In particular, mesityltriarylbismuthonium salts exhibit high oxidizing ability and high chemoselectivity in the competitive reactions between primary and secondary alcohols. Secondary, we developed highly efficient Bi(V)-based cationic photoinitiators for the first time. Photoirradiation of triaryl(1-pyrenyl)bismuthonium salts in acetonitrile afforded triarylbismuthanes and pyrene, accompanied by the generation of protic acids. Triaryl(1-pyrenyl)bismuthonium hexafluoroantimonates have proven to behave as efficient photoinitiators for the cationic polymerization of oxiranes and a vinyl ether, affording the corresponding polymers in good yields within a short photoirradiation time. During the search of sensitizers, which were anticipated to photoinitiate the Bi-mediated cationic polymerization, we designed new classes of porphyrins bearing phosphorus and sulfur substituents at the meso position. Finally, we successfully prepared several meso-phosphorylporphyrins and meso-sulfinylporphyrins, and elucidated their structures, optical properties, and electrochemical properties in detail.

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  • Synthesis of Hypervalent Organobismuth-oxo Complexes and Application to Oxidation

    Grant number:14540494

    2002 - 2003

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for Scientific Research (C)

    Awarding organization:Japan Society for the Promotion of Science

    MATANO Yoshihiro

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    Grant amount:\3500000 ( Direct Cost: \3500000 )

    A systematic series of triarylbismuthane oxides were prepared by treatment of the corresponding triarylbismuth dichlorides with excess water in the presence of two equivalents of potassium tert-butoxide. We disclosed the structures, thermal stability, and reactivity of this class of compounds. The bismuthane oxides exist as a dimeric, hydrated, or oligomeric form, depending on the structure of the aryl ligands attached to the bismuth center. It was found that the bismuthane oxides are thermally unstable and readily decompose to give triarylbismuthanes as the major products. Among the insoluble bismuth-derived byproducts, we successfully characterized the structure of a diarylbismuthinic anhydride by X-ray crystallography. It also was found that the oxidizing ability of the bismuthane oxides is much higher than those of lighter pnictogen counterparts, and is significantly enhanced by introducing ortho-substituents onto the aryl ligands. Based on this finding, we developed a new efficient method for alcohol oxidation using a triarylbismuth dichloride/DBU system, where primary and secondary alcohols were readily oxidized to the corresponding carbonyl compounds in good yields under mild conditions. In this system, the remarkably high substituent effects on the oxidizing ability were observed. Thus, introduction of an electron-withdrawing substituent at the para position and a methyl group at the ortho position enhances the rate of oxidation.

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  • Design of Fine Acid Base Catalysts and their Utility in Selective Organic Synthesis

    Grant number:13853003

    2001 - 2005

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for Scientific Research (S)

    Awarding organization:Japan Society for the Promotion of Science

    MARUOKA Keiji, OOI Takashi

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    Grant amount:\123890000 ( Direct Cost: \95300000 、 Indirect Cost:\28590000 )

    In this research project, we focused our attention on the rational design of truly efficient acid/base catalysts for the development of synthetic processes in order to achieve the high reactivity and selectivity, not observable by ordinary, acid/base catalysts. In the sophisticated Lewis acid chemistry, a new, chiral bidentate Ti(IV) complex was successfully designed and can be utilized for simultaneous coordination to aldehyde carbonyls, thereby allowing the precise enantioface discrimination of such carbonyls for a new catalytic, practical enantioselective allylation of aldehydes with allyltributyltin. This chiral bidentate Ti(IV) complex has been successfully applied to asymmetric 1, 3-dipolar cycloaddition of nitrones or diazoacetates. On the other hand, phase transfer catalysis is a very useful approach that typically involves simple experimental operations, mild reaction conditions, inexpensive and environmentally benign reagents and solvents, and the large-scale reactions. Accordingly, structurally rigid, chiral spiro ammoniurn salts derived from commercially available (S)- or (R)-binaphthol have been designed as new C_2-symmetric chiral phase transfer catalysts and successfully applied to the highly efficient, catalytic enantioselective synthesis under mild phase transfer conditions. Quite recently, we have successfully designed simplified, yet very active chiral phase transfer catalysts for practical asymmetric synthesis of α-alkyl- and α,α-dialkylamino acids. In addition, chiral, helical-type phase transfer catalysts were newly designed for effecting asymmetric Strecker reaction for large-scale production of sterically hindered α-alkylamino acids. A bowl-shaped organometallic host, tris(2, 6-diphenylbenzyl)-silyl, -germyl, and -tin compounds can be prepared, and applied to selective organic transformations.

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  • DEVELOPMENT AND APPLICATIONS OF BISMUTH YLIDES AND BISMUTH IMIDES IN ORGANIC SYNTHESIS

    Grant number:12640516

    2000 - 2001

    System name:Grants-in-Aid for Scientific Research

    Research category:Grant-in-Aid for Scientific Research (C)

    Awarding organization:Japan Society for the Promotion of Science

    MATANO Yoshihiro

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    Grant amount:\3500000 ( Direct Cost: \3500000 )

    In this research project, I aimed to utilize the characteristics of hypervalent organobismuth compounds in organic synthesis and to develop new synthetic tools based on bismuth ylides (Ar_3Bi=CRR') and bismuth imides (Ar_3Bi=NR). (1) New methods for the synthesis of stabilized bismuth ylides and bismuth imides were established, and their structures and reactivities have been disclosed. Bismuth imides bearing an acyl or a sulfonyl group on the imido nitrogen atom were prepared by the metathesis reaction, and stabilized bismuth ylides were synthesized by the addition reaction of the imides with electron-deficient acetylenes. X-ray crystallographic analyses of these compounds have elucidated that the bismuth(V)-carbon and bismuth(V)-nitrodgen bonds possess a highly polarized, single bond character. Additionally, systematic comparisons of the structures of bismuth imides with those of the lighter 15th group element counterparts were made for the first time. (2) New cyclization methods by use of bismuth ylides and by bismuth imides have been developed. For instance, the reaction of alkynylbismuthonium salts with a suitable nucleophile generates bismuth ylides of the type Ar_3Bi=C=CRR', which subsequently undergo cyclization with elimination of triarylbisrnuthane to give cyclopentenes and 2,5-dihydrofurans. Stabilized bismuth ylides also undergo cyclization by heat or in the presence of a copper catalyst to afford oxazoles. The driving force of these transformations is the high leaving ability of the triarylbismuthonio group. (3) A new method for the selective synthesis of organobismuth compounds bearing a styryl group was established. They underwent radical polymerization to afford soluble polystyrenes bearing bismuth substitutes. (4) During the course of studies on the synthesis of bismuth imides, a new and convenient method for the preparation of bismuth oxides has been developed, and further studies on this class of compounds are now in progress.

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  • ビスマス-窒素、酸素および硫黄二重結合を有する高原子価有機ビスマス化合物の化学

    Grant number:11120224

    1999

    System name:科学研究費助成事業

    Research category:特定領域研究(A)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\1000000 ( Direct Cost: \1000000 )

    1.本課題平成11年度においては、形式的なビスマス=窒素二重結合を有する高原子価有機ビスマス化合物、ビスマスイミド、およびその軽元素類縁体の化学を中心に検討を進めてきた。
    2.オルト位にメチル基もしくはメトキシ基を有するアリール基(ο-トリル基、ο-アニシル基)を用いてビスマス=窒素二重結合を速度論的に安定化することにより、様々なN-アシルおよびN-スルホニルトリアリールビスマスイミドを合成、単離した。また、同様の手法を用いて合成したN-スルホニルトリアリールアンチモンイミドが単量体として存在することを、X線結晶構造解析により初めて明らかにした。一連の15族元素由来のイミドの構造解析および理論計算の検討により、中心元素の周期が下がるに連れ、イミド結合の単結合性が増加し、ビスマス-窒素結合は極めて分極した単結合とみなせることが明かとなった。
    3.合成したN-アシルビスマスイミドの基本的な反応性を調べた結果、様々な基質との反応においてトリアリールビスムトニオ基が良好な脱離基として作用することを見いだした。これは15族元素の中でもビスマスに特徴的な振る舞いである。さらに、電子欠乏型アルキンであるアセチレンジカルボン酸ジエステルとの反応では、イミド窒素のマイケル付加、ビスムトニオ基の転位を経由してビスマスイリドが生成することを見いだした。本反応で得られたイリドは、高度に官能基化されたアルキリデン部位が負電荷を効率良く非局在化できるため、熱的に極めて安定化であり、本反応は安定型ビスマスイリドの新しい合成法と見なすことができる。

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  • ビスマス-窒素および酸素二重結合を有する高原子価有機ビスマス化合物の化学

    Grant number:10133225

    1998

    System name:科学研究費助成事業

    Research category:特定領域研究(A)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\1000000 ( Direct Cost: \1000000 )

    1. 本課題平成10年度においては、ビスマス=窒素二重結合を有する高原子価有機ビスマス化合物であるビスマスイミドの化学を中心に検討を進めてきた。
    2. オルト位にメチル基もしくはメトキシ基を有するアリール基(o-トリル基、o-アニシル基、メシチル基)がビスマス=窒素二重結合を速度論的に安定化することを見いだし、これを基にN-アシルおよびN-スルホニルトリアリールビスマスイミドを空気中でも安定に取り扱える化合物として合成、単離した。いくつかの化合物についてX線結晶構造解析を行った結果、ビスマス中心は歪んだ正四面体構造を取り、ビスマスー窒素の結合距離は既知のビスマスー窒素単結合の距離に近いことが明かとなった。また、N-アシル体ではカルボニル酸素が、N-スルホニル体ではスルホニル酸素がそれぞれビスマス中心の近傍に存在することがら、酸素原子のビスマス原子への分子内配位もこの結合の化学的安定化に大きく寄与していると思われる。N-アシル体は対応するN-スルホニル体に比べて熱的に不安定であった。
    3. 合成したN-アシルビスマスイミドの基本的な反応性を調べた結果、これらのイミドがホスフィンに対しN-アシルナイトレン等価体として、アルコールやチオールに対し酸化剤として振るまうことが明かとなった。例えばエタノールやイソプロパノールはN-アシルビスマスイミドにより室温でアセトアルデヒドおよびアセトンにそれぞれ酸化される。このような温和な酸化力は15族元素の中でもビスマスに特異的なものである。

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  • 原子価異性を鍵段階とするオン/オフ型機能性有機ビスマス化合物の構築

    Grant number:09740469

    1997 - 1998

    System name:科学研究費助成事業

    Research category:奨励研究(A)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\2000000 ( Direct Cost: \2000000 )

    1. 本課題平成10年度においては、複数のビスマス原子を分子内に有する有機ビスマス化合物の機能化をめざし、ひとつの展開として非イオン型水溶性ビスマス化合物を合成した。さらに、ビスマス原子上にキラリティを有するビスムチンおよびビスムトニウム化合物の合成法を確立し、キラルなビスマス化合物の基本的な物性を明らかにした。
    2. 非イオン型水溶性ビスマス化合物は例えば造影剤や抗菌剤としての利用が期待されているが、これまでその合成例はなかった。芳香環にN,N-ビス(ヒドロキシエチル)アミノスルホニル基を有するトリアリールビスムチンを合成してその水溶性を調べた結果、オルトおよびパラ位に同官能基を持つビスムチンが中性条件下で高い水溶性を示すことが明かとなった。さらに、昨年度の本研究課題で確立した手法-スルホニル基のポリオルトリチオ化-を本系に適用して、上記官能基を有するフェニレン架橋型オリゴビスムチン(ビスマス原子;2〜4個)をワンポットで合成し、その水溶性について評価した。
    3. ビスマス原子上のキラリティは学術的にも興味が持たれるが、今回、ビスマス上にキラリティを有する非対称テトラアリールビスムトニウム塩の合成法を確立した。オルト位にオキサゾリン置換基を有するビスムトニウム塩の場合、^1H-NMRではビスマス上のキラリティを反映したジアステレオトピックなシグナルが観測されるが、このシグナルをVT-NMRにより追跡することで、ビスマス上における立体化学的な挙動と対イオンや溶媒の極性との関係を明らかにした。

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  • ビスマス-窒素および-ケイ素結合を有する高原子価有機ビスマス化合物の化学

    Grant number:09239225

    1997

    System name:科学研究費助成事業

    Research category:重点領域研究

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\1000000 ( Direct Cost: \1000000 )

    1.本課題平成9年度においては、ビスマス=炭素およびビスマス=窒素二重結合を有する高原子価有機ビスマス化合物-ビスマスイリドおよびビスマスイミド-の化学を中心に検討を進めた。
    2.2-オキソアルキリデン型ビスマスイリドは1,2-ジカルボニル化合物と低温で円滑に反応するが、生成物の構造は基質の骨格に大きく依存することが明かとなった。すなわち、鎖状ケトエステルとの反応では2,3-二置換エポキシドが、オルトキノンとの反応では3-ヒドロキシトロポンが、さらにベンジルとの反応では非対称1,3-ジケトン由来のエノラートが生成する。いずれの反応においてもトリフェニルビスマス基は中性の良好な脱離基として作用し、遷移状態における立体的混み合いの違いが各反応経路に大きな差を与えているものと思われる。
    3.オルト位に適当な配位性官能基を導入することによりビスマスイミドを空気中でも安定に取り扱える化合物として単離し、X線結晶構造解析によりその構造を明らかにした。もとめられたビスマス=窒素結合の距離は単結合のそれに近いこと、配位性官能基がビスマス中心と大きく相互作用していることから、超原子価構造がこの結合の化学的安定化に大きく寄与していると思われる。
    4.ビスマス原子上に異なる3つのアリール基を持つ非対称トリアリールビスマスイミドの合成に成功した。近傍にオキサゾリン置換基を有する場合、H-NMRにおいてビスマス上のキラリティに反映すると思われるジアステレオトピックなシグナルを与える。これらのキラリティの評価は構造化学的に大変興味が持たれるところであり、現在その詳細について検討中である。

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  • 共役型官能基を有する新規ビスムトニウム化合物の構築と機能性材料への応用

    Grant number:08740492

    1996

    System name:科学研究費助成事業

    Research category:奨励研究(A)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\1000000 ( Direct Cost: \1000000 )

    1.本課題においては、非対称アリールビスムトニウム塩と求核種との反応における置換基効果を明らかにした。また、分子内にキラル中心を二つ持つ非対称テトラアリールビスムトニウム塩の化学について基礎的な検討を行った。さらに、共役型多環芳香族官能基を有するトリアリールビスムチンの合成に成功した。
    2.アリールビスムトニウム塩の反応性を知る自的で、アニシル、チオアニシル、トリル基を有する非対称アリールビスムトニウム塩を合成し、チオラート、フェノキシド、スルフィナ-トとの反応における置換基効果を検討した結果、求核種はより電子不足なアリール基と優先的に反応することが明らかとなった。
    3.機能性材料の中で光学活性化合物の果たす役割は重要である。我々は既に全てのアリール基が異なるテトラアリールビスムトニウム塩の一般的な合成方法を確立しているが、今回、キラル中心であるビスマス原子の異性化挙動に関する基礎的な知見を得る目的で、対イオンもしくはリガンドに別のキラル中心を持つジアステレオマ-の合成を行い、いずれも安定な化合物として単離することに成功した。定量化までには至っていないが、現在核磁気共鳴法を用いてその異性化挙動を検討中である。
    4.多環共役置換基を有するビスマス化合物はこれまでほとんど報告例がなかったが、ハロビスムチンとアリールリチウム、もしくはビスムチドとヨードアレーンとのカップリング反応によりアンセトラセン、フェナントレン置換基を持つビスムチンの合成に初めて成功した。吸収スペクトルの測定により、これらの化合物におけるビスマス置換基の置換特性が明らかとなった。今後、対応するジクロリド、オニウム塩も含めて多環共役系置換基を有する一連のビスマス化合物の構造と分子内電荷移動状態の相関をさらに詳細に検討する予定である。

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  • 特異な官能基導入反応の開発とその機構解明をめざした新規ビスムトニウム化合物の構築

    Grant number:07740496

    1995

    System name:科学研究費助成事業

    Research category:奨励研究(A)

    Awarding organization:日本学術振興会

    俣野 善博

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    Grant amount:\1000000 ( Direct Cost: \1000000 )

    1.ビスマスが高原子価状態において示す特異的な挙動は、構造、理論および合成化学の領域において興味深い研究対称として注目を集めている。本課題においては、最近までその姿が全く知られていなかったアルケルビスムトニウム塩およびビスマス上にキラル中心を持つ非対称テトラアリールビスムトニウム塩の一般的な合成法を初めて確立し、その構造と反応性について詳細に検討した。
    2.トリフェニルビスマスジフルオリドを、塩化メチレン中ルイス酸存在下、シリルシアニド、アルケニル錫と順次反応させると、アルケニルトリフェニルビスムトニウム塩が安定な結晶として得られる。X線結晶構造解析の結果、ビスマス中心は歪んだ正四面体型構造を取り、対イオンとの相互作用は比較的弱いことが明かとなった。アルケニルビスムトニウム塩はスルフィン酸塩およびパラジウム錯体と容易に反応してアルケニル基を優先的にトランスファーする。塩基との反応においては、系中でフリーなアルキリデンカルベンを発生し、スチレンが共存する場合にはトリフェニルビスムタンの脱離を伴って対応するシクロプロパンを与える。
    上の反応系において、アルケニル錫の代わりにアリール錫を炭素求核剤として用いると、非対称アリールトリフェニルビスムトニウム塩が高収率で得られる。この手法を利用して、全てのアリール基が異なる非対称テトラアリールビスムトニウム塩の合成に成功した。この化合物はビスマス原子上にキラル中心を有しており、異性化挙動の解明や機能性材料への応用など、様々な展開が期待できる。

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  • 新しいタイプのビスムトニウム化合物の構築およびそれを利用した合成反応の開発

    Grant number:06740480

    1994

    System name:科学研究費助成事業

    Research category:奨励研究(A)

    Awarding organization:日本学術振興会

    俣野 喜博

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    Grant amount:\1200000 ( Direct Cost: \1200000 )

    1.ビスマスは安定元素の中で最も重い元素であり、しばしば軽元素の化学からは予測できない興味深い挙動を示す。本課題においては、最近までその姿が全く知られていなかったオキソアルキルビスムトニウム塩および準安定型ビスムトニウムイリドの一般的な合成法を初めて確立し、その構造と反応性について詳細に検討した。
    2.トリアリールビスマスジフルオリドをルイス酸存在下、シリルエノールエーテルもしくはシロキシシクロプロパンと反応させると、2-あるいは3-オキソアルキルトリアリールビスムトニウム塩が安定な結晶として得られる。X線結晶構造解析の結果、これらのオニウム塩の安定化にはアルキル鎖のカルボニル基の空間配置が重要な役割を果たしていることが明かとなった。また、それぞれのオニウム塩は求核種との反応においてアルキル基を選択的にトランスファーする。
    3.2-オキソアルキルビスムトニウム塩は、低温下適当な塩基を作用させると、準安定型のトリアリールビスムトニウムイリドに変換される。得られたイリドはアリデヒド、アジリジンとの反応によりα,β-エポキシケトン、α,β-アジリジノケトンとトリアリールビスムチンを良好な収率で与えるが、このような反応形式は同族のリン、ヒ素、アンチモンの類縁体には見られず、この反応においてビスマスの特異性が顕著に現れていることが明かとなった。
    4.上記の結果は、高原子価有機ビスマス化合物の持つユニークな化学性の一面を明らかにするものであり、今後さらに各種ビスムトニウム化合物の合成、構造および反応性について系統的に研究を進めていく予定である。

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  • 高原子価有機ビスマスオキシド・ビスムトニウム塩の特性を活かした新しい増炭・酸化反応の開発

    Grant number:05740392

    1993

    System name:科学研究費助成事業

    Research category:奨励研究(A)

    Awarding organization:日本学術振興会

    俣野 善博

      More details

    Grant amount:\1000000 ( Direct Cost: \1000000 )

    1.ビスマスは安定元素の中で最も重い元素であり、しばしば軽元素の科学からは予測できない興味深い振舞いを示す。本課題においては、今日まで未開拓の化学種であったビスマスオキシド、ビスムトニウム塩の合成法を確立し、さらにその構造および科学挙動について検討した。
    2.ビスマスオキシドの合成を目的としたトリフェニルビスムチンの直接酸化は極めて多彩な結果をもたらした。中でもオゾン/トルエン系による酸化では、予期せぬ生成物であるリトフェニルビスマスジフォルメートが定量的に得られた。一方、ヨードソベンゼンによる酸化では目的とするトリフェニルビスマスオキシドが溶液状態で定量的に生成する。この化学種は同族のリン、ヒ素、アンチモンのオキシドとは異なり各種アルコーを効率よく酸化した。
    3.ビスムトニウム塩、特にアルキル-ビスマス結合を有するビスムトニウム塩の一般的合成法はこれまで全く知られていなかったが、トリアリールビスマスジフルオリド・ルイス酸・シリルエノ-エウエーテルの組み合わせによる2-オキソアルキルビスムトニウム塩の効率的な合成に成功した。得られたビスムトニウム塩の構造をX線解析により確定し、その化学的挙動を知るために種々の求核種との反応について検討した。その結果、4つのリガンドの中で2-オキソアルキル基がアシルカチオン等価体として選択的に求核試剤にトランスファーされることが明らかとなった。
    4.上記の結果は、高原子価ビスマス化合物のもつユニークな一面を明らかにするものであり、今後さらに各種誘導体の合成・構造・反応性について検討していく予定である。

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Teaching Experience

  • グリーンケミストリー概説

    2023
    Institution name:新潟大学

  • 科学・技術と社会

    2023
    Institution name:新潟大学

  • 有機化学I

    2023
    Institution name:新潟大学

  • 新素材の物性

    2022
    Institution name:新潟大学

  • 化学コロキウム

    2022
    Institution name:新潟大学

  • 理学スタディ・スキルズ

    2022
    Institution name:新潟大学

  • 統合化学入門

    2022
    Institution name:新潟大学

  • 大型機器分析技術

    2022
    Institution name:新潟大学

  • 数理物質科学の最前線

    2022
    Institution name:新潟大学

  • 化学英語

    2021
    -
    2022
    Institution name:新潟大学

  • 有機合成方法論II

    2021
    Institution name:新潟大学

  • 有機物質合成論

    2021
    Institution name:新潟大学

  • 課題研究 a

    2020
    Institution name:新潟大学

  • 課題研究 b

    2020
    Institution name:新潟大学

  • 先端科学技術総論

    2020
    Institution name:新潟大学

  • 理学スタディ・スキルズ

    2018
    -
    2022
    Institution name:新潟大学

  • 自然科学総論Ⅰ

    2018
    Institution name:新潟大学

  • 有機化学Ⅱ

    2017
    Institution name:新潟大学

  • 課題研究

    2017
    Institution name:新潟大学

  • 化学英語

    2017
    -
    2022
    Institution name:新潟大学

  • 総合力アクティブ・ラーニング

    2017
    -
    2019
    Institution name:新潟大学

  • 安全教育

    2016
    Institution name:新潟大学

  • 日本事情自然系A

    2015
    Institution name:新潟大学

  • 数理物質科学特定研究ⅡA(化学)

    2015
    Institution name:新潟大学

  • 有機機器分析

    2014
    Institution name:新潟大学

  • 有機化学演習

    2014
    Institution name:新潟大学

  • 有機物質合成論

    2014
    -
    2021
    Institution name:新潟大学

  • 化学入門

    2014
    -
    2020
    Institution name:新潟大学

  • 有機化学II

    2014
    -
    2016
    Institution name:新潟大学

  • 化学実験

    2014
    -
    2015
    Institution name:新潟大学

  • 数理物質科学特定研究Ⅰ(化学)

    2014
    Institution name:新潟大学

  • 数理物質科学演習Ⅰ(化学)

    2014
    Institution name:新潟大学

  • 社会を支える有機化学

    2013
    Institution name:新潟大学

  • 有機合成方法論Ⅱ

    2013
    -
    2017
    Institution name:新潟大学

  • 課題研究(化学科)

    2013
    -
    2016
    Institution name:新潟大学

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