担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/cplu.201900087

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その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/cplu.201900087

担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/anie.201800471

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/anie.201510734

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/tcr.201402101

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担当区分：筆頭著者,　責任著者   記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：社団法人 有機合成化学協会  

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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掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/asia.202401370

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掲載種別：研究論文（学術雑誌）  

Inclusion of a heteroatom to the phosphole ring is a promising strategy to intrinsically modulate the optical properties of phosphole derivatives. We report on a series of 2-aryl-3H-1,3-benzazaphosphole oxides that were efficiently prepared via sequential C−P cross-coupling, dehydrative [3+2] cycloaddition, and ring-oxidation reactions. The inclusion of one nitrogen atom into the benzophosphole framework caused red shifting of the absorption and emission maxima, reflecting the greater stabilization of the LUMO level. 2-(2-Hydroxyphenyl)benzazaphosphole oxide underwent excited state intramolecular proton transfer and emitted a weak fluorescence from the excited state of the N−H tautomer.

DOI： 10.1002/chem.202400807

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

<jats:title>Abstract</jats:title>
<jats:p>We report herein an improved method for the quantitative preparation of free bases of 5,10,15,20-tetraaryl-5,15-diazaporphyrinoid (TADAP) using Me3SiBr–MeOH to treat the corresponding zinc(II) complexes. Metallation of the free base with HSiCl3 followed by Si–X metathesis with SbF3 and redox reactions afforded difluorosilicon(IV) complexes of TADAP.</jats:p>

DOI： 10.1093/bulcsj/uoad022

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掲載種別：研究論文（学術雑誌）  

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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掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

DOI： 10.1246/bcsj.20230071

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：World Scientific Pub Co Pte Ltd  

<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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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

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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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

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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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：World Scientific Pub Co Pte Lt  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

DOI： 10.1246/cl.210218

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

DOI： 10.1021/acs.jpcb.1c02360

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：World Scientific Pub Co Pte Lt  

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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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

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.

DOI： 10.1002/ajoc.201900085

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/hc.21456

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

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.

DOI： 10.1021/acs.joc.8b00087

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/acs.joc.8b00030

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/acs.joc.8b00030

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/ange.201800471

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担当区分：最終著者,　責任著者   掲載種別：研究論文（学術雑誌）  

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.

DOI： 10.1246/bcsj.20180123

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：World Scientific  

DOI： 10.1142/S1088424618500529

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

© The Royal Society of Chemistry 2018. 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.

DOI： 10.1039/c8dt01503a

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記述言語：英語   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/jacs.7b09424

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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.

DOI： 10.1039/c7dt01839h

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

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.

DOI： 10.1021/ja203822q

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

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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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/cplu.201700051

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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.

DOI： 10.1002/asia.201700204

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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.

DOI： 10.1002/ajoc.201600612

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

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.

DOI： 10.1021/acs.chemrev.6b00460

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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.

DOI： 10.1002/ejoc.201600611

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

© 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.

DOI： 10.1039/c5dt03362d

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/jp510903a

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

© 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.

DOI： 10.1021/acs.joc.5b00541

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：World Scientific  

DOI： 10.1142/S1088424615500509

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担当区分：最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH Verlag  

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.

DOI： 10.1002/chem.201405482

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/hc.21188

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/ejic.201301132

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201304626

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp410436f

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/ol401994e

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

Carboxyphenylethynyl-substituted diazaporphyrin has been synthesized to assess the utility of diazaporphyrins in dye-sensitized solar cells for the first time. The diazaporphyrin-sensitized TiO₂ cell exhibited photocurrent generation in the visible region of 400–700 nm together with a power conversion efficiency of 0.08%.

DOI： 10.1246/cl.130212

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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).

DOI： 10.1021/ol4000982

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201203047

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/ic301835c

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/asia.201200492

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：社団法人 有機合成化学協会  

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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その他リンク： https://jlc.jst.go.jp/DN/JALC/10005669843?from=CiNii

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201200463

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201103843

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ja210205v

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp208775x

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：論文集(書籍)内論文   出版者・発行元：SPRINGER-VERLAG BERLIN  

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.

DOI： 10.1007/128_2011_167

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WORLD SCI PUBL CO INC  

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.

DOI： 10.1142/S1088424611004087

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/cl.2011.919

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jp2030208

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ja203822q

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

DOI： 10.1246/bcsj.20100326

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-BLACKWELL  

DOI： 10.1002/cssc.201100029

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-BLACKWELL  

DOI： 10.1002/anie.201007065

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ACADEMIC PRESS INC ELSEVIER SCIENCE  

DOI： 10.1016/j.jcis.2011.01.066

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記述言語：英語   出版者・発行元：American Institute of Physics  

Solid-state nuclear magnetic resonance (NMR) has been applied to "amorphous" active layers consisting of donor-acceptor self-assembled composites in organic solar cells. Several stoichiometric supramolecular complexation states as well as the charge-transfer states are revealed by the solid-state NMR, which have been difficult to access by conventional spectroscopy. The spectra show clear correlation between local self-assembled supramolecular structures and the organic solar cell performances.

DOI： 10.1063/1.3565237

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-BLACKWELL  

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

DOI： 10.1002/hc.20708

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.201102782

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c0ee00482k

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

DOI： 10.1039/c1jm11531f

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jp911141s

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER FRANCE-EDITIONS SCIENTIFIQUES MEDICALES ELSEVIER  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jp1004049

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ol100926q

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jp102486b

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

DOI： 10.1246/cl.2010.448

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/adma.200903056

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ol100114j

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WALTER DE GRUYTER GMBH  

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.

DOI： 10.1351/PAC-CON-09-08-05

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jp910832a

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jo902060b

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：TAYLOR & FRANCIS LTD  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

DOI： 10.1039/c0cc00709a

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/om900745t

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jp907288h

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/ja901166a

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ar900075e

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ol901194m

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

6014

DOI： 10.1021/jp902001z

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp902623g

J-GLOBAL

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/ja8096465

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PubMed

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/anie.200900542

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/chem.200901378

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

DOI： 10.1039/b819255n

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

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.

DOI： 10.1246/bcsj.81.1621

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jp807991k

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Phthalocyanines with high peripheral substitutions and free from potential contamination by regioisomers have been synthesized and evaluated as photosensitizers for dye-sensitized solar cell applications. Each of the sterically hindered precursor compounds was accomplished by Suzuki-Miyaura cross-coupling reactions with the arylchloride and corresponding boronic acids. Metal free phthalocyanine-sensitized solar cells showed no photocurrent generation due to its low excited singlet state (LUMO) compared with the conduction band of TiO(2). Upon zinc metalation, the LUMO level of the phthalocyanine was pushed up, and this variation afforded an exergonic free energy change for electron injection. The zinc phthalocyanine-sensitized solar cell displayed 0.57% power conversion efficiency (eta) and 4.9% maximal IPCE in the near infrared region. More importantly, the cell prepared with and without the presence of chenodeoxycholic acid revealed no difference in the power conversion efficiency. This implies that the well-known aggregation tendency of phthalocyanines that is considered to enhance the self-quenching of the phthalocyanine excited singlet state is effectively suppressed by the high degree of substitutions. The significance of the driving force for electron injection and the distance between the dye core and the TiO(2) surface is also highlighted for devising high performance phthalocyanine photosensitizers.

DOI： 10.1039/b803272f

CiNii Article

CiNii Books

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

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%).

DOI： 10.1246/cl.2008.846

CiNii Article

CiNii Books

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/cphc.200800270

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/om800099h

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/jo800532n

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/ol8005453

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

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.

DOI： 10.1021/jp710400p

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/cssc.200700138

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ol7029118

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/ejoc.200701008

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ja076709o

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ja807742g

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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.

DOI： 10.1002/chem.200801017

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ja710542e

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/asia.200800229

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/chem.200702053

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

5323

DOI： 10.1021/jp805122z

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.200700446

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jp0726079

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jo070822f

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

DOI： 10.1016/j.cplett.2007.07.013

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp072075w

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp071604t

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

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.

DOI： 10.1016/j.tetlet.2007.02.085

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jp067290b

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ol070556s

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.200600835

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/asia.200700191

Scopus

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp068893q

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/ol622763

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/la061527d

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ja0640039

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ol061506a

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/adma.200600312

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/jo0605748

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/la0533314

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/om060300a

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp061524+

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

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.

DOI： 10.1016/j.tet.2005.05.109

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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.

DOI： 10.1039/b513707a

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/la0533314

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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.

DOI： 10.1002/chem.200500610

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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.

DOI： 10.1021/jp044725r

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/adma.200401770

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/jp0537409

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/jp044725r

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/chem.200500610

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jo0485740

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/om0494115

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/jo0492721

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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.

DOI： 10.1039/b404690k

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記述言語：英語   出版者・発行元：Elsevier  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）  

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.

DOI： 10.1021/ic0110575

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Thieme  

DOI： 10.1055/s-2002-23536

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ic0110575

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ja003623l

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記述言語：日本語   出版者・発行元：The Society of Synthetic Organic Chemistry, Japan  

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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その他リンク： https://jlc.jst.go.jp/DN/JALC/00122798045?from=CiNii

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：GEORG THIEME VERLAG KG  

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.

DOI： 10.1055/s-2001-14565

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ja010584k

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE SA  

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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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om000133t

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om000095d

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ic991120e

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE SA  

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.

DOI： 10.1016/S0022-328X(99)00506-9

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：GEORG THIEME VERLAG  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ic981334g

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/jo990690t

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om990252c

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om980914i

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry  

Triphenylbismuthonium 2-oxoalkylide 1, generated in situ from the corresponding onium salt 2 and base in THF at low temperatures, reacts with benzils 3 to give O-aroyl enolates of unsymmetrical 1,3-diketones 4 in moderate to good yields.

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om980184e

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om9804531

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

DOI： 10.1246/cl.1998.127

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry  

DOI： 10.1039/a801879k

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om980411c

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om9701377

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry  

DOI： 10.1039/a706338e

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om960320k

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/om9509709

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry  

DOI： 10.1039/cc9960002697

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

DOI： 10.1246/bcsj.69.2673

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

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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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/jo00119a056

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

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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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：GEORG THIEME VERLAG  

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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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

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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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

DOI： 10.1246/cl.1991.105

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

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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記述言語：英語   掲載種別：研究論文（学術雑誌）  

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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総ページ数：636   担当ページ：247–327   記述言語：英語 著書種別：学術書

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総ページ数：462   担当ページ：103–113   記述言語：日本語 著書種別：学術書

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記述言語：日本語   出版者・発行元：The Society of Physical Organic Chemistry, Japan  

2,5位に官能基を持つホスホール誘導体をピロールとの脱水縮合反応によりホスファトリピランへと変換したのち、 [3+1]型環化脱水縮合反応と引き続く酸化反応を行うことで、ポルフィリンのピロール骨格をホスホール骨格で置換した構造を持つホスファポルフィリンを合成することに初めて成功した。講演では、合成の詳細とホスファポルフィリンの芳香族性、光物性、電気化学的特性などの諸物性について報告する。

DOI： 10.11494/kisoyuki.18.0.17.0

CiNii Article

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記述言語：日本語   出版者・発行元：技術情報協会  

CiNii Article

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開催年月日： 2009年

記述言語：日本語  

ホスホールは高い電子受容能を持つ複素環化合物であるが、化学的・熱的に安定な新規パイ共役ホスホールの構築をめざして、ホスホール環の両ベータ位にナフタレン環が縮環した三種類の誘導体を設計し、対応するナフタレン、アセナフテン、アセナフチレンジインよりチタナサイクルを経由する方法を用いて効率よく合成することに成功した。得られた化合物の構造-物性相関を系統的に調べたので、その結果についても報告する。

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開催年月日： 2008年10月

記述言語：日本語  

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開催年月日： 2008年10月

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開催年月日： 2008年9月

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開催年月日： 2008年9月

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開催年月日： 2008年9月

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開催年月日： 2008年9月

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開催年月日： 2008年9月

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開催年月日： 2008年9月

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開催年月日： 2008年9月

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開催年月日： 2008年5月

記述言語：日本語  

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開催年月日： 2008年3月

記述言語：日本語  

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開催年月日： 2008年3月

記述言語：日本語  

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開催年月日： 2008年3月

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開催年月日： 2008年3月

記述言語：日本語  

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開催年月日： 2008年3月

記述言語：日本語  

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開催年月日： 2008年3月

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開催年月日： 2008年3月

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開催年月日： 2008年3月

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開催年月日： 2008年3月

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開催年月日： 2008年3月

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開催年月日： 2008年3月

記述言語：日本語  

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開催年月日： 2008年

記述言語：日本語  

ビチオフェンが縮環したベンゾ[&lt;I&gt;c&lt;/I&gt;]ホスホール誘導体の合成と、その構造、光物性、および電気化学的特性について報告する。アリールエチニル基が導入されたビチオフェン誘導体と低原子価チタン試剤から調製されるチタナシクロペンタジエンを、系中でジクロロフェニルホスフィンと反応させることにより、縮環モードが異なる３つのタイプのビチオフェン縮環ベンゾ[&lt;I&gt;c&lt;/I&gt;]ホスホールを合成した。各種測定ならびにモデル化合物に対する理論計算を行った結果、得られた化合物の構造、吸収特性、発光特性、および電気化学特性はビチオフェン環の縮環モードおよびリン上の置換基の種類に強く依存することが明らかとなった。

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開催年月日： 2007年12月

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開催年月日： 2007年9月

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開催年月日： 2007年9月

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開催年月日： 2007年9月

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開催年月日： 2007年9月

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開催年月日： 2007年9月

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開催年月日： 2007年9月

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開催年月日： 2007年9月

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開催年月日： 2007年9月

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開催年月日： 2007年8月

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開催年月日： 2007年8月

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開催年月日： 2007年3月

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開催年月日： 2007年3月

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開催年月日： 2007年3月

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開催年月日： 2007年3月

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開催年月日： 2007年3月

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開催年月日： 2007年3月

記述言語：日本語  

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