2022/12/10 更新

写真a

ホシノ ノリヒサ
星野 哲久
HOSHINO Norihisa
所属
教育研究院 自然科学系 特任准教授
職名
特任准教授
外部リンク

学位

  • 博士(理学) ( 2009年3月   筑波大学 )

研究キーワード

  • 分子磁性

  • 単分子磁石

  • 単一次元鎖磁石

  • 分子性強誘電体

  • 分子導体

  • 電子移動共役スピン転移

  • 分子性熱電材料

  • 分子性触媒

研究分野

  • ナノテク・材料 / 基礎物理化学  / 分子磁性

  • ナノテク・材料 / 無機・錯体化学  / 錯体化学

経歴(researchmap)

  • 新潟大学   自然科学系   特任准教授

    2022年4月 - 現在

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  • 東北大学   多元物質科学研究所   助教

    2011年4月 - 2022年3月

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  • 筑波大学   数理物質科学等支援室   準研究員

    2009年4月 - 2011年3月

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  • 三菱化学株式会社   研究員

    2002年4月 - 2006年5月

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経歴

  • 新潟大学   教育研究院 自然科学系   特任准教授

    2022年4月 - 現在

学歴

  • 筑波大学   数物科学研究科   物質創成先端化学専攻

    2006年4月 - 2009年3月

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    国名: 日本国

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  • 東北大学   理学研究科   化学専攻

    2000年4月 - 2002年3月

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    国名: 日本国

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  • 東北大学   理学部   化学科

    1996年4月 - 2000年3月

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    国名: 日本国

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所属学協会

委員歴

  • 1st. Asian Conference on Molecule-based Magnets 国内組織委員  

    2021年3月   

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  • 43rd. International Conference on Coordination Chemistry 実行委員  

    2018年8月   

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  • 第68回錯体化学討論会 実行委員  

    2018年7月   

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  • PHyMセミナー「機能性分子固体の最前線」 世話人  

    2017年11月   

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  • 第11会分子科学討論会 実行委員  

    2017年9月   

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  • The 15th International Conference on Molecule-based Magnets 実行委員  

    2016年9月   

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  • PHyM若手フォーラム2014国内会議 実行委員  

    2014年12月   

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  • 化学系学協会東北大会 実行委員  

    2013年9月   

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▶ 全件表示

 

論文

  • Ferroelectrics Coupled with Unidirectional Rotation in Liquid Crystals 査読

    Jianyun Wu, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    The Journal of Physical Chemistry C   126 ( 8 )   3864 - 3871   2022年3月

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    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.jpcc.1c10313

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  • Heterospin frustration in a metal-fullerene-bonded semiconductive antiferromagnet 査読

    Yongbing Shen, Mengxing Cui, Shinya Takaishi, Hideyuki Kawasoko, Kunihisa Sugimoto, Takao Tsumuraya, Akihiro Otsuka, Eunsang Kwon, Takefumi Yoshida, Norihisa Hoshino, Kazuhiko Kawachi, Yasuhiko Kasama, Tomoyuki Akutagawa, Tomoteru Fukumura, Masahiro Yamashita

    Nature Communications   2022年1月

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    掲載種別:研究論文(学術雑誌)  

    DOI: 10.1038/s41467-022-28134-w

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  • Electrostatic versus van der Waals Interactions in an n-Type Semiconducting Dianionic Naphthalenediimide Derivative with CnH2n+1NH3+ (n = 1–16) 査読

    Ayumi Kawasaki, Takashi Takeda, Norihisa Hoshino, Wakana Matsuda, Shu Seki, Tomoyuki Akutagawa

    The Journal of Physical Chemistry C   2021年10月

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    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.jpcc.1c05176

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  • Crystal Structures and Physical Properties of (M+)(Crown Ethers)x(TCNQ)y Salts with M+ = Li+, Na+, K+, Rb+, and Cs+ 査読

    Kohei Sambe, Norihisa Hoshino, Takashi Takeda, Takayoshi Nakamura, Tomoyuki Akutagawa

    Crystal Growth & Design   21 ( 10 )   5928 - 5942   2021年10月

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    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.cgd.1c00812

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  • Ion polarisation-assisted hydrogen-bonded ferroelectrics in liquid crystalline domains 査読

    Guohao Yuan, Yuko Kimura, Takayuki Kobayashi, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    Chemical Science   12 ( 40 )   13520 - 13529   2021年10月

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

    An alkylamide-substituted (−NHCOC<sub>10</sub>H<sub>21</sub>) hydrogen-bonded dibenzo[18]crown-6 derivative (1) was prepared to stabilise the ionic channel structure in a discotic hexagonal columnar (Col<sub>h</sub>) liquid crystal.

    DOI: 10.1039/d1sc03301h

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  • Donor-Type Nickel–Dithiolene Complexes Fused with Bulky Cycloalkane Substituents and Their Application in Molecular Conductors 査読

    Kazuya Kubo, Mamoru Sadahiro, Sonomi Arata, Norihisa Hoshino, Tomofumi Kadoya, Tomoyuki Akutagawa, Reizo Kato, Jun-ichi Yamada

    Crystals   11 ( 10 )   1154 - 1154   2021年9月

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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:MDPI AG  

    The effects of substituents on the arrangement of metal–dithiolene complexes based on π-conjugated systems, which are extensively used to synthesize various functional materials, have not been studied adequately. New donor-type nickel–dithiolene complexes fused with bulky cycloalkane substituents [Ni(Cn-dddt)2] (C5-dddt = 4a,5,6,6a-pentahydro-1,4-benzodithiin-2,3-dithiolate; C6-dddt = 4a,5,6,7,8,8a-hexahydro-1,4-benzodithiin-2,3-dithiolate; C7-dddt = 4a,5,6,7,8,9,9a-heptahydro-1,4-benzodithiin-2,3-dithiolate; and C8-dddt = 4a,5,6,7,8,9,10,10a-octahydro-1,4-benzodithiin-2,3-dithiolate) were synthesized in this study. All the complexes were crystallized in cis-[Ni(cis-Cn-dddt)2] conformations with cis-oriented (R,S) conformations around the cycloalkylene groups in the neutral state. Unique molecular arrangements with a three-dimensional network, a one-dimensional column, and a helical molecular arrangement were formed in the crystals owing to the flexible cycloalkane moieties. New 2:1 cation radical crystals of [Ni(C5-dddt)2]2(X) (X = ClO4− or PF6−), obtained by electrochemical crystallization, exhibited semiconducting behaviors (ρrt = 0.8 Ω cm, Ea = 0.09 eV for the ClO4− crystal; 4.0 Ω cm, 0.13 eV for the PF6− crystal) under ambient pressure due to spin-singlet states between the dimers of the donor, which were in accordance with the conducting behaviors under hydrostatic pressure (ρrt = 0.2 Ω cm, Ea = 0.07 eV for the ClO4− crystal; 1.0 Ω cm, 0.12 eV for the PF6− crystal at 2.0 GPa).

    DOI: 10.3390/cryst11101154

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  • Further investigations of the crystal-to-crystal phase transition of a [2]pseudorotaxane composed of ferrocene-terminated dialkylammonium and dibenzo[24]crown-8-ether 査読

    Yuji Suzaki, Yugo Fukuchi, Hiroko Tadami, Take-aki Koizumi, Kohtaro Osakada, Tomohito Ide, Masaki Horie, Norihisa Hoshino, Tomoyuki Akutagawa

    CrystEngComm   23 ( 34 )   5944 - 5952   2021年9月

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

    A pseudorotaxane with different or mixed counter anions undergoes thermal phase transition, which is related to the interaction between the counter anion and macrocyclic component.

    DOI: 10.1039/d1ce00457c

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  • Ferroelectricity of Hydrogen-Bonded Azobenzene Derivatives 査読

    Jianyun Wu, Qingyang Zhu, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    ACS Applied Electronic Materials   3 ( 8 )   3521 - 3529   2021年8月

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    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/acsaelm.1c00462

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  • Ionic Conductivities Induced by the Partial Solvent Molecule Removal from Diruthenium(II,III) Adamantanecarboxylate Salts 査読

    Norihisa Hoshino, Tomoyuki Akutagawa

    Crystal Growth & Design   21 ( 8 )   4640 - 4646   2021年8月

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    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.cgd.1c00496

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  • Effective Na<sup>+</sup>-Binding Ability and Molecular Assembly of an Alkylamide-Substituted Penta(ethylene)glycol Derivative 査読

    Shinya Seto, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    Journal of Physical Chemistry B   125 ( 23 )   6349 - 6358   2021年6月

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    掲載種別:研究論文(学術雑誌)  

    A new amphiphilic penta(ethylene glycol) derivative (1) bearing two hydrogen-bonding -CONHC14H29 chains was prepared. Compound 1 exhibited ion-recognition abilities for Na+ and K+, and its properties were compared with those of the macrocyclic [18]crown-6. Although both compound 1 and [18]crown-6 have six ether oxygen atoms (-OC2H2-), the Na+-binding ability of the former was much higher than that of the latter. K+-binding ability of cyclic [18]crown-6 was much higher than its Na+-binding ability, while the reverse was true for acyclic compound 1. Single-crystal X-ray structural analysis of Na+·1·B(Ph)4-·(hexane)2 at 100 K revealed the existence of a wrapped Na+-coordination by six ether and one carbonyl oxygen atoms of 1, which was further stabilized by intramolecular N-H···O= hydrogen-bonding interactions. The complex phase transition during glass (G) formation and recrystallization was confirmed in the thermal cycle of Na+·1·B(Ph)4-, whose molten state showed two kinds of liquid phases, Na+-complexed (Na+·1) + B(Ph)4- and completely dissociated Na+ + 1 + B(Ph)4-. The Na+ conductivity of the molten state was 2 orders of magnitude higher than that of the G phase.

    DOI: 10.1021/acs.jpcb.1c03188

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  • Quantitative analysis of the formation mechanism of tightly bound rubber by using carbon-coated alumina nanoparticles as a model filler 査読

    Yasuto Hoshikawa, Rei Kawaguchi, Keita Nomura, Hidenobu Akahane, Takafumi Ishii, Mariko Ando, Norihisa Hoshino, Tomoyuki Akutagawa, Hiroshi Yamada, Takashi Kyotani

    Carbon   173   870 - 879   2021年3月

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    掲載種別:研究論文(学術雑誌)  

    Using carbon-coated alumina nanoparticles as a model filler for styrene-butadiene rubber (SBR), rubber composites with different carbon surface chemistry were prepared and the bound rubber thus formed in each composite was analyzed in relation to the carbon surface chemistry. The present approach provides quantitative understanding of the rubber-carbon interface at the molecular level and thereby the formation mechanism of tightly bound rubber during a mixing process with SBR is proposed as follows. At first, the strong physisorption of SBR occurs and almost all the filler surface (99.8% of the total surface) is covered with a single-molecule layer of physisorbed SBR. The polymer radicals formed in the process are then gradually allowed to react with the H-terminated edge sites on the exposed carbon surface (0.2% of the total surface) and the resulting free edge sites are chemically-bonded to the other polymer radicals to form the chemisorbed polymer. Moreover, the unique structure of the present composites makes it possible to analyze the state of tightly bound rubber with the conventional differential scanning calorimetry, which strongly suggests that the tightly bound rubber is indeed in a glassy state.

    DOI: 10.1016/j.carbon.2020.11.074

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  • Inversion Symmetry Breaking in Order–Disorder Transitions of Globular Ligands Coordinating to Cobalt(II) and Nickel(II) Bisacetylacetonato Complexes During Heating 査読

    Norihisa Hoshino, Tomoyuki Akutagawa

    Chemistry - A European Journal   27 ( 12 )   4064 - 4069   2021年2月

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    掲載種別:研究論文(学術雑誌)  

    Unexpected inversion-symmetry breaking was observed in the order–disorder phase transitions of [M(acac)2(abco)2] (1; M=Co2+, 2; Ni2+, acac−=2,4-pentanedionato, abco=1-azabicyclo-[2.2.2]-octane=quinuclidine) during heating. The isostructural, transition-free complexes [M(acac)2(cabco)2] (3; M=Co2+, 4; Ni2+, cabco=3-chloro-1-azabicyclo-[2.2.2]-octane=3-chloroquinuclidine) were also studied for comparison. Complexes 1 and 2 crystallized in ordered phases in the centrosymmetric I2/m space group at 100 K, whereas they crystallized in disordered phases in the non-symmetric I2 space group at 300 K. The 60° step rotation disordering of the abco ligands was observed in the electron density maps of 1 and 2, which was consistent with the transition enthalpies estimated by differential scanning calorimetry (DSC). Gradual phase transitions were observed for 1 and 2 by DSC and powder X-ray diffraction (PXRD) at approximately 225 K. The inversion-symmetry disordering was likely induced by the local pseudo-symmetry of the abco ligands, increasing from trigonal to hexagonal and the increased steric repulsion pathways among them.

    DOI: 10.1002/chem.202004492

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  • Dynamic structural reconstruction of (guanidinium<sup>+</sup>)<sub>2</sub>(benzene-1,4-disulfonate<sup>2−</sup>) host crystal by guest adsorption 査読

    Haruka Abe, Takahiro Kobayashi, Norihisa Hoshino, Takashi Takeda, Yasutaka Suzuki, Jun Kawamata, Tomoyuki Akutagawa

    CrystEngComm   23 ( 5 )   1149 - 1157   2021年2月

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    掲載種別:研究論文(学術雑誌)  

    Guanidinium (G+) and benzene-1,4-disulfonate (BDS2−) form a rigid electrostatic cation-anion crystal lattice, which undergoes an interesting dynamic structural reconstruction through guest adsorption-desorption processes with H2O, pyrrole (Pyrr), pyrazine (Pyz), thiophene (TP), pyridine (Py), 1,4-dioxane (Diox), or aniline (Ani). The host lattice of bis(guanidinium)benzene-1,4-disulfonate, (G+)2(BDS2−), which does not contain void spaces initially, changed to host-guest crystals of (G+)2(BDS2−)·(guest)xupon guest adsorption (x= 1, 2, and 3). The cation-anion electrostatic N-H+⋯−O3S- hydrogen bonds between theG+cation andBDS2−dianion formed tightly bound two-dimensional (2D) structures. These layers are connected by perpendicularBDS2−dianions, forming the guest adsorption crystalline pores. The adsorption-desorption isotherm for Diox at 298 K indicated the formation of (G+)2(BDS2−)·(Diox)3, which was consistent with the single-crystal X-ray structural analysis. Single crystals of (G+)2(BDS2−)·(Py-H2O)2consist of two hydrogen-bonded [(G+)2(BDS2−)]2bilayers connected by theBDS2−dianions, forming crystalline pores that accommodate 2 Py guest molecules. The H2O molecules in (G+)2(BDS2−)·(Py-H2O)2are lodged in the intralayer, leading to the [(G+)2(BDS2−)⋯(H2O)2⋯(G+)2(BDS2−)] hydrogen-bonded bilayer. The electrostatic cation-anion host lattice of (G+)2(BDS2−) responded to the guest adsorption-desorption cycle by a dynamic structural reconstruction. A guest adsorption of polar Ani into (G+)2(BDS2−) host changed the crystal symmetry from centricP1̄ to acentricP21of (G+)2(BDS2−)·(Ani)3

    DOI: 10.1039/d0ce01616k

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  • Ferroelectric columnar assemblies from the bowl-to-bowl inversion of aromatic cores 査読

    Shunsuke Furukawa, Jianyun Wu, Masaya Koyama, Keisuke Hayashi, Norihisa Hoshino, Takashi Takeda, Yasutaka Suzuki, Jun Kawamata, Masaichi Saito, Tomoyuki Akutagawa

    Nature Communications   12 ( 1 )   768   2021年2月

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    掲載種別:研究論文(学術雑誌)  

    Organic ferroelectrics, in which the constituent molecules retain remanent polarization, represent an important topic in condensed-matter science, and their attractive properties, which include lightness, flexibility, and non-toxicity, are of potential use in state-of-the-art ferroelectric devices. However, the mechanisms for the generation of ferroelectricity in such organic compounds remain limited to a few representative concepts, which has hitherto severely hampered progress in this area. Here, we demonstrate that a bowl-to-bowl inversion of a relatively small organic molecule with a bowl-shaped π-aromatic core generates ferroelectric dipole relaxation. The present results thus reveal an unprecedented concept to produce ferroelectricity in small organic molecules, which can be expected to strongly impact materials science.

    DOI: 10.1038/s41467-021-21019-4

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  • Crystal Lattice Design of H2O-Tolerant n-Type Semiconducting Dianionic Naphthalenediimide Derivatives 査読

    Haruka Abe, Ayumi Kawasaki, Takashi Takeda, Norihisa Hoshino, Wakana Matsuda, Shu Seki, Tomoyuki Akutagawa

    Journal of the American Chemical Society   143 ( 2 )   1046 - 1060   2021年1月

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    掲載種別:研究論文(学術雑誌)  

    Dianionic bis(propionate)-naphthalenediimide (PCNDI2-) formed simple 2:1 cation-anion salts of (M+)2(PCNDI2-)·(H2O)n (M+ = Li+, Na+, K+, Rb+, and Cs+), which exhibited reversible H2O adsorption-desorption behavior because of the presence of their electrostatically binding crystal lattices. The maximum H2O adsorption amounts (n) for M+ = Li+, Na+, K+, Rb+, and Cs+ were 0.25, 6.0, 4.0, 6.0, and 2.0, respectively, whereas the reversible gate-opening (gate-closing) H2O adsorption-desorption isotherms were observed at 273 and 298 K, except for M+ = Li+. High ionic conductivities of around 10-4-10-5 S cm-1 were observed in M+ = Na+ and K+ salts, whereas short-range thermal fluctuations occurred in large cations of M+ = Rb+ and Cs+. The change in the electrostatic lattice energy for M+ = Na+ and K+ salts during the H2O adsorption-desorption cycles was significantly larger than those for M+ = Rb+ and Cs+. Therefore, the Na+ and K+ salts had a considerably flexible electrostatic crystal lattice with a large amplitude of lattice modulation during the H2O sorption cycle. In contrast, the lattice modulation for M+ = Rb+ and Cs+ salts involved a low magnitude of ion displacements, forming a relatively rigid cation-anion electrostatic crystal lattice. The flash-photolysis time-resolved microwave conductivity and transition absorption spectroscopy results revealed the high electron mobility of H2O-adsorbed thin films, wherein the crystallized H2O molecules did not act as electron-trapping sites. The values of electron mobility increased in the order of Cs+ ≈ Rb+ > K+ > Na+ > Li+.

    DOI: 10.1021/jacs.0c11545

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  • A synthetic ion channel with anisotropic ligand response 査読

    Takahiro Muraoka, Daiki Noguchi, Rinshi S. Kasai, Kohei Sato, Ryo Sasaki, Kazuhito V. Tabata, Toru Ekimoto, Mitsunori Ikeguchi, Kiyoto Kamagata, Norihisa Hoshino, Hiroyuki Noji, Tomoyuki Akutagawa, Kazuaki Ichimura, Kazushi Kinbara

    Nature Communications   11 ( 1 )   2924   2020年12月

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    掲載種別:研究論文(学術雑誌)  

    Biological membranes play pivotal roles in the cellular activities. Transmembrane proteins are the central molecules that conduct membrane-mediated biochemical functions such as signal transduction and substance transportation. Not only the molecular functions but also the supramolecular properties of the transmembrane proteins such as self-assembly, delocalization, orientation and signal response are essential for controlling cellular activities. Here we report anisotropic ligand responses of a synthetic multipass transmembrane ion channel. An unsymmetrical molecular structure allows for oriented insertion of the synthetic amphiphile to a bilayer by addition to a pre-formed membrane. Complexation with a ligand prompts ion transportation by forming a supramolecular channel, and removal of the ligand deactivates the transportation function. Biomimetic regulation of the synthetic channel by agonistic and antagonistic ligands is also demonstrated not only in an artificial membrane but also in a biological membrane of a living cell.

    DOI: 10.1038/s41467-020-16770-z

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  • Dielectric and gas adsorption/desorption properties of: X-Li(Pc) having one-dimensional channels surrounded by Pc<sup>-</sup>columns 査読

    Miki Nishi, Norihisa Hoshino, Shin Ichiro Noro, Hitoshi Fujimoto, Tomoyuki Akutagawa, Masaki Matsuda

    CrystEngComm   22 ( 44 )   7528 - 7531   2020年11月

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    掲載種別:研究論文(学術雑誌)  

    A one-dimensional channel system x-Li(Pc), composed of π-radical Pc-, was investigated. Crystal structure analysis revealed that this channel surrounded by Li(Pc) columns is flexible, and gas adsorption/desorption measurements showed selective adsorption/desorption properties. Along with Li+ motion, specific dielectric properties induced by a guest species within the channel were also observed.

    DOI: 10.1039/d0ce01157f

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  • Synthesis, Structure and Physical Properties of (trans-TTF-py2)1.5(PF6)·EtOH: A Molecular Conductor with Weak CH∙∙∙N Hydrogen Bondings 査読

    Shohei Koyama, Morio Kawai, Shinya Takaishi, Masahiro Yamashita, Norihisa Hoshino, Tomoyuki Akutagawa, Manabu Kanno, Hiroaki Iguchi

    Crystals   10 ( 12 )   1081 - 1081   2020年11月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:MDPI AG  

    The studies of crystal structures with hydrogen bonds have been actively pursued because of their moderate stabilization energy for constructing unique structures. In this study, we synthesized a molecular conductor based on 2,6-bis(4-pyridyl)-1,4,5,8-tetrathiafulvalene (trans-TTF-py2). Two pyridyl groups were introduced into the TTF skeleton toward the structural exploration in TTF-based molecular conductors involved by hydrogen bonds. In the obtained molecular conductor, (trans-TTF-py2)1.5(PF6)·EtOH, short contacts between the pyridyl group and the hydrogen atom of the TTF skeleton were observed, indicating that hydrogen bonding interactions were introduced in the crystal structure. Spectroscopic measurements and conductivity measurement revealed semiconducting behavior derived from π-stacked trans-TTF-py2 radical in the crystal structure. Finally, these results are discussed with the quantified hydrogen bonding stabilization energy, and the band calculation of the crystal obtained from density functional theory calculation.

    DOI: 10.3390/cryst10121081

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  • Interfacial nanostructuring of poly(vinylidene fluoride) homopolymer with predominant ferroelectric phases 査読

    Chang Fu, Huie Zhu, Norihisa Hoshino, Tomoyuki Akutagawa, Masaya Mitsuishi

    Langmuir   36 ( 46 )   14083 - 14091   2020年11月

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    掲載種別:研究論文(学術雑誌)  

    Facile preparation of poly(vinylidene fluoride) (PVDF) homopolymer nanoparticles (NPs) with monodispersed size distribution and predominant ferroelectric phases was done in an interfacial nonsolvent (water/methanol)-solvent (dimethylformamide (DMF))-polymer (PVDF) ternary system using two interfacial nanoassembly methods. First, a fluidic liquid-liquid interface consisting of two miscible solvents was created by introducing nonsolvent (water) under the PVDF solution. After the interface was created, the interface moved up to the DMF phase direction; PVDF NPs were produced through nonsolvent-induced phase separation. As the water content decreased in the nonsolvent by mixing with methanol, PVDF structures changed from nanoparticles with 252 nm average diameter (PVDF NP-1) to a porous membrane through membrane-wrapped NPs. The phenomena were found to be related to the mutual affinity of solvent, nonsolvent, and PVDF. When an additional external force was introduced to the water-DMF-PVDF system through magnetic stirring (reprecipitation method), smaller PVDF NPs with 61.4 nm diameter were obtained (PVDF NP-2). Both the as-prepared PVDF NPs were demonstrated with the predominant ferroelectric (electroactive (EA)) phase up to 97-98% among crystalline phases, which is apparently the highest value ever reported for PVDF homopolymer NPs. It is noteworthy that PVDF NP-2 showed a higher β phase ratio than that of PVDF NP-1, as proved using Fourier transform infrared (FT-IR) spectroscopy. Also, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) measurements revealed that PVDF NP-1 exhibited higher crystallinity and that PVDF NP-2 underwent a well-separated two-step phase transition under heating. Results suggest that controlling interface formation with DMF and water plays a crucial role in manipulating ferroelectric PVDF nanostructures in terms of crystallinity and the ferroelectric β phase-to-γ phase ratio.

    DOI: 10.1021/acs.langmuir.0c02667

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  • Contrasting temperature dependences of isostructural one-dimensional ferroelectric crystals NH4HSO4 and RbHSO4 in terms of thermal conductivities 査読

    Norihisa Hoshino, Tomoyuki Akutagawa

    The Journal of Chemical Physics   153 ( 19 )   194503 - 194503   2020年11月

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    掲載種別:研究論文(学術雑誌)   出版者・発行元:AIP Publishing  

    DOI: 10.1063/5.0028153

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  • Titania Nanofilms from Titanium Complex-Containing Polymer Langmuir-Blodgett Films 査読

    Shunsuke Yamamoto, Asami Ono, Jun Matsui, Norihisa Hoshino, Tomoyuki Akutagawa, Tokuji Miyashita, Masaya Mitsuishi

    Langmuir   36 ( 35 )   10371 - 10378   2020年9月

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    掲載種別:研究論文(学術雑誌)  

    This paper proposes a method of fabricating low-dimensional TiO2 nanofilms at room temperature under ambient pressure conditions. The titanium-containing polymer complex Ti-p(DDA/acac) was synthesized by reacting an amphiphilic copolymer (p(DDA/acac)) with a titanium complex. Its ultrathin films were prepared using the Langmuir-Blodgett (LB) technique. The monolayer was found to be free from hydrolysis and cross-linking side reactions, even at the air-water interface. The transferred LB films (nanosheets) were oxidized by ultraviolet irradiation at room temperature. The photo-oxidized material has an amorphous and porous structure with subnanometer-scale controllability (0.18 nm per layer). Photocatalytic performance was demonstrated by converting multilayered LB films of Ti-(DDA/acac) and the silicon-containing polymer p(DDA/SQ) into ultrathin hetero-multilayers of TiO2 and SiO2 under UV-O3 treatment. The scalability affords a uniform photopattern formation of photo-oxidized TiO2 films over several hundreds of micrometers.

    DOI: 10.1021/acs.langmuir.0c01446

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  • Switching of Electron and Ion Conductions by Reversible H2O Sorption in n-Type Organic Semiconductors 査読

    Haruka Abe, Ayumi Kawasaki, Takashi Takeda, Norihisa Hoshino, Wakana Matsuda, Shu Seki, Tomoyuki Akutagawa

    ACS Applied Materials and Interfaces   12 ( 33 )   37391 - 37399   2020年8月

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    掲載種別:研究論文(学術雑誌)  

    Polar H2O molecules generally act as trapping sites and suppress the electron mobility of n-Type organic semiconductors, making chemical design of H2O-Tolerant and responsive n-Type semiconductors an important step toward multifunctional electron-ion coupling devices. The introduction of effective electrostatic interactions between potassium ions (K+) and carboxylate (-COO-) anions into the electron-Transporting naphthalenediimide I-framework enables the design of high-performance H2O-Tolerant n-Type semiconductors with a reversible H2O adsorption-desorption ability, where the electron mobility and K+ ionic conductivity were coupled with the reversible H2O sorption behavior. The reversible H2O adsorption into the crystals enhanced the electron mobility from 0.04 to 0.28 cm2 V-1 s-1, whereas the K+ ionic conductivity decreased from 3.4 × 10-5 to 4.7 × 10-7 S cm-1. Because this reversible electron-ion conducting switch is responsive to H2O sorption behavior, it is a strong candidate for H2O gating carrier transport systems.

    DOI: 10.1021/acsami.0c09501

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  • Dynamics of Chiral Cations in Two-Dimensional CuX<sub>4</sub>and PbX<sub>4</sub>Perovskites (X = Cl and Br) 査読

    Masaki Takahashi, Norihisa Hoshino, Kohei Sambe, Takashi Takeda, Tomoyuki Akutagawa

    Inorganic Chemistry   59 ( 16 )   11606 - 11615   2020年8月

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    掲載種別:研究論文(学術雑誌)  

    Chiral organic ammonium cations ((R)-2-methylphenethylammonium (R-MPhA) and (R)-3,7-dimethyloctylammonium (R-DMOA)) cations were combined with [MX4]2- anions (M = Cu and Pb, X = Cl and Br) to form two-dimensional (2D) perovskites: (R-MPhA)2CuCl4 (1a), (R-MPhA)2CuBr4 (1b), (R-DMOA)2CuCl4 (2a), (R-DMOA)2CuBr4 (2b), (R-DMOA)2PbCl4 (2c), and (R-DMOA)2PbBr4 (2d). The point shearing of the MX4 octahedron formed 2D perovskite layers, which were sandwiched by the bilayer molecular assembly of chiral organic ammonium cations. We found that the flexible and polar organic R-MPhA and R-DMOA cations in the 2D perovskites played an important role in the phase transition behavior and dielectric responses. Salts 2a-2d showed similar solid-solid (S1-S2) phase transitions, for which the temperatures decreased in the order of CuCl4 (2a) > PbCl4 (2c) > CuBr4 (2b) > PbBr4 (2d). The occupation volume of one R-DMOA per MX4 octahedron determined the dynamic crystalline space for the motional freedom of chiral ammonium in the 2D perovskite layer. Although thermally activated dielectric fluctuations were observed in salts 2a, 2b, and 2c, only an order-disorder-type dielectric phase transition was observed in salt 2d. Interband optical transitions were observed in the CuCl4 and CuBr4 2D perovskites, whereas sharp exciton absorptions were observed in the 2D PbCl4 and PbBr4 layers in perovskite salts 2c and 2d.

    DOI: 10.1021/acs.inorgchem.0c01404

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  • Ferroelectric low-voltage ON/OFF switching of chiral benzene-1,3,5-tricarboxamide derivative 査読

    Jianyun Wu, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    Journal of Materials Chemistry C   8 ( 30 )   10283 - 10289   2020年8月

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    掲載種別:研究論文(学術雑誌)  

    The phase transition behaviour, molecular assemblies, and dielectric responses of an N,N′,N′′-trialkylbenzene-1,3,5-tricarboxamide derivative bearing chiral (S)-3,7-dimethyloctyl chains (S-3BC) were compared with those of an N,N′,N′′-trioctadecylbenzene-1,3,5-tricarboxamide derivative (3BC) bearing achiral -CONHC14H29 chains. Chiral S-3BC showed a similar phase transition behaviour to achiral 3BC, and ferroelectric polarization-electric field (P-E) hysteresis curves were observed in the discotic hexagonal columnar (Colh) liquid crystal phase. Interestingly, the magnitudes of Pr and Et values of S-3BC were 5.5-times larger and 13-times smaller than those of 3BC because of the introduction of the chiral alkyl chains, indicating a useful method to obtain low voltage ON/OFF ratios for the switching device. Much stronger N-H⋯O hydrogen-bonding interactions were observed in S-3BC than in 3BC because of much shorter π-stacking distance and blue-shift of the intermolecular asymmetrical N-H vibrational band in the former, which effectively decreased the potential energy barrier for the dipole inversion between N-H⋯O and O⋯H-N orientations and the Et value.

    DOI: 10.1039/d0tc02414g

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  • Mixed Columnar Assembly of Ferroelectric and Antiferroelectric Benzene Derivatives Bearing Multiple-CONHC14H29 Chains 査読

    Jianyun Wu, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    Journal of Physical Chemistry B   124 ( 32 )   7067 - 7074   2020年8月

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    掲載種別:研究論文(学術雑誌)  

    The discotic hexagonal columnar (Colh) liquid crystalline phases of simple benzene derivatives bearing-CONHC14H29 chains at the 1-, 3-, and 5-positions (3BC) and 1-, 2-, 4-, and 5-positions (4BC) display ferroelectricity and antiferroelectricity, respectively. The phase transition behavior, molecular assembly structures, dielectric response, and ferroelectric properties of their mixed crystals [(3BC)1-x(4BC)x] were evaluated to clarify the nanoscaling effect on the collective inversion of the one-dimensional (1D) N-H···O= hydrogen bonding interaction observed in the (3BC)∞ chain. A small quantity of 4BC doped into 3BC (x ≤ 0.03) maintained the ferroelectric polarization-electric field response (P-E) in the (3BC)1-x(4BC)x chains, where the antiferroelectric 4BC molecules in the ferroelectric 3BC column act as a pinning potential site for dipole inversion. On the contrary, a relatively large amount of 4BC doping (x ≥ 0.1) forms a domain separation state between the hydrogen-bonded (3BC)∞ and (4BC)∞ columns, in which the ferroelectric P-E hysteresis completely disappeared. The correlation length for the appearance of ferroelectricity in the 1D column was estimated to be ∼40 nm in the Colh liquid crystalline phase of 3BC.

    DOI: 10.1021/acs.jpcb.0c03365

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  • Emergence of electrical conductivity in a flexible coordination polymer by using chemical reduction 査読

    Kentaro Fuku, Momoka Miyata, Shinya Takaishi, Takefumi Yoshida, Masahiro Yamashita, Norihisa Hoshino, Tomoyuki Akutagawa, Hiroyoshi Ohtsu, Masaki Kawano, Hiroaki Iguchi

    Chemical Communications   56 ( 61 )   8619 - 8622   2020年8月

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    掲載種別:研究論文(学術雑誌)  

    A flexible coordination polymer with a naphthalenediimide core exhibited reversible desorption-adsorption of solvent molecules and an enhancement of electrical conductivity (∼10-7 S cm-1) upon chemical reduction using hydrazine.

    DOI: 10.1039/d0cc03062g

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  • Dynamics and Structural Diversity of Li<sup>+</sup>(Crown Ether) Supramolecular Cations in Electrically Conducting Salts 査読

    Kohei Sambe, Norihisa Hoshino, Takashi Takeda, Takayoshi Nakamura, Tomoyuki Akutagawa

    Journal of Physical Chemistry C   124 ( 25 )   13560 - 13571   2020年6月

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    掲載種別:研究論文(学術雑誌)  

    Li+([12]crown-4)2(TCNQ)2 (1), Li+([15]crown-5)(TCNQ)2 (2a and 2b), and Li+([18]crown-6)(TCNQ)2·(H2O)2 (3) salts (TCNQ = 7,7,8,8-tetracyano-p-quinodimethane) were prepared and examined in terms of crystal structures, dielectric constants, magnetic susceptibilities, and electrical conductivities. The dynamic behavior of the small Li+ was easily activated inside the cavities of [15]crown-5 and [18]crown-6. In salt 2a, a structural phase transition at 160 K is thermally activated by a change in the -CN···Li+···NC- coordination from an asymmetrical to a symmetrical environment. The phase-transition temperature for salt 2a is approximately 25 K lower than that for the isostructural Na+([15]crown-5)(TCNQ)2, indicating that the behavior of Li+ inside the [15]crown-5 cavity is considerably more dynamic than that of Na+ in the same situation. Crystal polymorphs 2a and 2b are observed for Li+([15]crown-5) supramolecular cations, where the two-dimensional intermolecular interactions of TCNQs in salts 2a and 2b are constructed by the spanning-overlap mode of the π-dimers and π-tetramers, respectively. The packing periodicity in the latter salt is twice that in the former, and this structural difference prevents the structural phase transition for salt 2b. In salt 3, the orientational disorder of Li+ inside the cavity of the [18]crown-6 is a combination of the dynamic behavior of Li+ itself and that of Li+-coordinated polar H2O molecules, which are evidenced by two types of dielectric relaxation. Li+ is considerably smaller than Na+, allowing it to form a dynamic Li+···O coordination environment.

    DOI: 10.1021/acs.jpcc.0c02686

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  • Structural Modulation of Electrically Conducting TCNQ Salts Using Na<sup>+</sup>(crown ether) Supramolecular Cations 査読

    Kohei Sambe, Norihisa Hoshino, Takashi Takeda, Takayoshi Nakamura, Tomoyuki Akutagawa

    Crystal Growth and Design   20 ( 6 )   3625 - 3634   2020年6月

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    掲載種別:研究論文(学術雑誌)  

    The single crystals of Na+([12]crown-4)2(TCNQ)2 (1), Na+([15]crown-5)(TCNQ)2 (2), Na+([18]crown-6)(TCNQ)2.5 (3), and Na+([24]crown-8)(TCNQ)2 (4) (TCNQ = 7,7,8,8-tetracyano-p-quinodimethane) were prepared and defined by single-crystal X-ray structural analyses. Of these, salts 1 and 2 showed structural phase transitions at 320 and 185 K, respectively, upon heating. According to differential scanning calorimetry, temperature (T)-dependent crystal structures, and dielectric measurements, the motional freedom and orientation change of the spherical sandwich-type Na+([12]crown-4)2 supramolecular cation activated the phase transition. Furthermore, a symmetry change in salt 2 from the low-T Pc to the high-T P21/c was observed and a symmetry change in the Na+···NC-coordination environment is the origin of the structural phase transition at 185.4 K. Conversely, no distinct structural phase transitions were observed for salts 3 and 4. In all of the crystals, the πdimer of the partially reduced TCNQ formed a segregated Ï€-stacking structure that interacted further by interdimer interactions to form electrically conducting TCNQ layers. Nonuniform and one-dimensional (1D) Ï€-stacking columns of TCNQ were observed in salts 1, 3, and 4, while two-dimensional (2D) spanning-overlap interdimer interactions were confirmed in salt 2. The electrical resistivity and activation energy of 2D salt 2 were 10-10000 and 2 times lower, respectively, than those of the 1D electronic systems of salts 1, 3, and 4.

    DOI: 10.1021/acs.cgd.0c00169

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  • Stable Ferromagnetic Crystal of Two-Dimensional Manganese-Chromium Oxalate with Supramolecular Cation 査読

    Kazuya Kubo, Masashi Yoshitake, Norihisa Hoshino, Shin ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura

    European Journal of Inorganic Chemistry   2020 ( 17 )   1670 - 1675   2020年5月

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    掲載種別:研究論文(学術雑誌)  

    A supramolecular cation of (m-FAni+)(tst-DCH[18]crown-6), where m-FAni+ and tst-DCH[18]crown-6 denote m-fluoroanilinium and trans-syn-trans-dicyclohexano[18]crown-6, respectively, was introduced into a ferromagnetic {[MnIICrIII(oxalate)3]–} layer to obtain a stable organic-inorganic hybridized crystal. The crystal structure of (m-FAni+)(tst-DCH[18]crown-6){[MnIICrIII(oxalate)3]–} was constructed by alternate stacking of a two-dimensional honeycomb layer of {[MnIICrIII(oxalate)3]–} and the supramolecular cations. Cyclohexyl moieties of tst-DCH[18]crown-6 penetrated the pores of the honeycomb layers, excluding solvent molecules in the crystal. The anionic layers showed ferromagnetic order of MnII and CrIII ions with S = 5/2 and S = 3/2 spins, respectively, at 5.5 K. Although the m-FAni+ showed disorder with respect to 180° rotation of the aryl ring, no significant anomaly was observed in the dielectric response, suggesting that the disorder is static.

    DOI: 10.1002/ejic.202000149

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  • Negative-to-Positive Thermal Conductivity Temperature Coefficient Transition Induced by Dynamic Fluctuations of the Alkyl Chains in the Layered Complex (C4H9NH3)2CuCl4 査読

    Norihisa Hoshino, Syunsaku Tamura, Tomoyuki Akutagawa

    Chemistry - A European Journal   26 ( 12 )   2610 - 2618   2020年2月

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    掲載種別:研究論文(学術雑誌)  

    A negative-to-positive transition of the temperature coefficients of thermal conductivity was found in the two-dimensional organic–inorganic layered complex (C4H9NH3)2CuCl4 (C4CuCl4) over the three structural phase transitions in the range 176–218 K. The coefficients of the low-temperature phases (85–200 K, α and β phases) were negative, as is typical for insulating crystals, whereas those of the high-temperature phases (200–300 K, γ and δ phases) were positive, as is typical for glasses and liquids. Single-crystal X-ray structure analyses revealed that the tilted C4H9NH3+ chains in the α and β phases were fully outstretched in the δ phase, and the interlayer distances between the CuCl42− planes increased significantly. The γ phase was an intermediate phase that crystallized with an incommensurate structure, in which the CuCl42− sheets formed wave-like structures consisting of connected alternating regions of β-like and δ-like moieties. In the γ and δ phases, thermal fluctuations of the C4H9NH3+ chains were found in the electron density maps; however, powder X-ray diffraction (PXRD) data indicated that the thermal expansion of the C4H9NH3+ layers was restricted by the rigid CuCl42− layers. This situation was considered to induce glass-like thermal conducting properties in the material, such as a positive temperature coefficient. The mean free path of the phonons estimated by using the thermal conductivities and heat capacities was a function of T−1 in the range 85–200 K, as would be expected for crystals, whereas it was approximately constant in the range 200–300 K, which is typical of glasses. In addition, the existence of soft vibration modes in the two-dimensional perovskite CuCl42− sheets was revealed by analysis of the incommensurate crystal structure of the γ phase. These low-energy vibration modes were believed to induce the cooperative phase transitions, along with the thermal fluctuations and van der Waals interactions in the C4H9NH3+ layers.

    DOI: 10.1002/chem.201904553

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  • Tunnel magnetocapacitance in Fe/MgF<sub>2</sub> single nanogranular layered films 査読

    Robin Msiska, Shusaku Honjo, Yuki Asai, Masashi Arita, Atsushi Tsurumaki-Fukuchi, Yasuo Takahashi, Norihisa Hoshino, Tomoyuki Akutagawa, Osamu Kitakami, Masaya Fujioka, Junji Nishii, Hideo Kaiju

    Applied Physics Letters   116 ( 8 )   2020年2月

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    掲載種別:研究論文(学術雑誌)  

    The tunnel magnetocapacitance (TMC) effect in two-dimensional single nanogranular layered Fe / MgF 2 films is investigated both experimentally and theoretically. We measured the frequency dependence of TMC ratios in a frequency range of 20 Hz-1 MHz and discovered that TMC ratios strongly depend on the frequency, reaching a peak value at a specific frequency. We observe that the largest TMC ratios occur at lower frequencies and that TMC values steadily reduce with increasing frequency. Notably, we achieved a maximum TMC ratio of 1.45%, which is the largest low-field TMC ever reported for granular films. A combination of the Debye-Fröhlich (DF) model and the Julliere formula is used to fit the experimental data to theory, and an excellent agreement between the calculated values and the experimental data is obtained. To perfectly fit the experimental data, the conventional DF model is extended to a composite model in which three capacitors (with three different relaxation times) are introduced. Our findings will give further insights into the exact mechanism of the TMC effect in nanogranular films and will open broader opportunities for device applications, such as magnetic sensors and impedance tunable devices.

    DOI: 10.1063/1.5139702

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  • Density and Dimensional Control of π-Electrons in Electrostatically Binding Naphthalenediimide Salts 査読

    Ayumi Kawasaki, Takashi Takeda, Norihisa Hoshino, Wakana Matsuda, Shu Seki, Tomoyuki Akutagawa

    Crystal Growth and Design   20 ( 2 )   1276 - 1284   2020年2月

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    掲載種別:研究論文(学術雑誌)  

    Dianionic bis(benzenesulfonate)-naphthalenediimide (BSNDI2-) formed simple 2:1 cation-anion salts of (NH4+)2(BSNDI2-) (1), (CH3NH3+)2(BSNDI2-) (2), (C2H5NH3+)2(BSNDI2-) (3), [(C2H5)2NH2+]2(BSNDI2-) (4), and [(C2H5)3NH+]2(BSNDI2-) (5). The thermal stability, crystal structure, electron transport properties, and dielectric response were evaluated for these systems in terms of π-electron density and dimensional crossover from two-dimensional (2D) and one-dimensional (1D) to zero-dimensional (0D) electronic structures. Systematic modification of the counter cations from NH4+ to simple alkylammoniums (CH3NH3+, C2H5NH3+, (C2H5)2NH2+, and (C2H5)3NH+) for BSNDI2- salts affected the packing π-density and dimensionality of NDI π-cores. All single crystals formed alternating cation-anion layers, where the intermolecular interactions in salts 1, 2, 3, 4, and 5 were observed as dense 2D brickstone, 1D column, 1D column, dilute 2D herringbone, and isolated 0D monomer arrangements, respectively. The π-electron occupation percentage in the unit cell of salts 1, 2, 3, 4, and 5 decreased in that order, at 96.2%, 87.8%, 83.8%, 78.8%, and 72.6%, respectively, where the intermolecular π-πinteraction between BSINDI2- anions was gradually diluted on increasing in the cation volume. The transfer integrals between the lowest unoccupied molecular orbital in salts 1-5 clearly indicated a dimensional crossover from 2D to 1D to 0D electronic structures. Flash-photolysis time-resolved microwave conductivity measurements of salts 1, 2, 3, and 4 helped determine the magnitude of electron carrier mobility, which followed the order 1 > 2 ≈ 3 ≈ 4. The dielectric response of salt 1 being an order of magnitude higher than those of salts 2-5 was associated with the protonic conductivity in the NH4+···-SO3- electrostatic hydrogen-bonding network layer. Simple cation exchange in dianionic BSNDI2- salts conventionally modified the intermolecular π-πinteractions in terms of dimensionality, magnitude, and electron transport properties.

    DOI: 10.1021/acs.cgd.9b01526

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  • Highly Proton-Conducting Mixed Proton-Transferred [(H<sub>2</sub>PO<sub>4</sub><sup>-</sup>)(H<sub>3</sub>PO<sub>4</sub>)]∞ Networks Supported by 2,2′-Diaminobithiazolium in Crystals 査読

    Guohao Yuan, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    Journal of Physical Chemistry C   2020年

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    掲載種別:研究論文(学術雑誌)  

    Hydrogen-bonding organic acid-base salts are promising candidates for the chemical design of high-performance anhydrous proton conductors. The simple molecular crystals between the I-planar molecules of 2,2′-diaminobithiazolium (DABT) derivative and hydrogen-bonding H3PO4 formed the proton-transferred salts with proton conductivities above â&circ;¼10-4 S cm-1 and anisotropic behavior. Controlling the crystallization condition facilitated the formation of binary salts between di-cationic H2DABT2+ and (H3PO4-)2 or mixed proton-transferred (H2PO4-)2(H3PO4)2 with different hydrogen-bonding networks, including one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) networks. The structural isomers of 2,2′-diamino-4,4′-bithiazolium (2,4-DABT) and 2,2′-diamino-5,5′-bithiazolium (2,5-DABT) formed a different type of packing structure even with the same crystal stoichiometry of (H2DABT2+)(H2PO4-)2 and/or (H2DABT2+)(H2PO4-)2(H3PO4)2 where the latter salt had different protonated species of H2PO4- and H3PO4 in the hydrogen-bonding network. Four and 10 protons per H2DABT2+ molecule (H+: Carrier concentration) were present in the (H2DABT2+)(H2PO4-)2 and (H2DABT2+)(H2PO4-)2(H3PO4)2 salts, respectively, which accounted for the highly proton-conducting behavior in the latter mixed protonated crystal. To design anhydrous intrinsic H+ conductors, both the mixed proton transfer state and uniform O-H···O= hydrogen-bonding interaction are essential factors that must be considered.

    DOI: 10.1021/acs.jpcc.9b10130

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  • Ferroelectricity of a Tetraphenylporphyrin Derivative Bearing -CONHC<sub>14</sub>H<sub>29</sub> Chains at 500 K 査読

    Jianyun Wu, Takashi Takeda, Norihisa Hoshino, Yasutaka Suzuki, Jun Kawamata, Tomoyuki Akutagawa

    Journal of Physical Chemistry C   123 ( 36 )   22439 - 22446   2019年9月

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    掲載種別:研究論文(学術雑誌)  

    Optical properties of porphyrin derivatives were used to fabricate an artificial light-harvesting system. The introduction of a N-H···O= hydrogen-bonding alkylamide chain (-CONHCnH2n+1) into a functional π-system is among the useful approaches to design multifunctional supramolecular assemblies. The tetraphenylporphyrin derivative bearing four -CONHC14H29 chains (1) shows the successive and reversible phase transition behavior of S1-S2 at 338 K, S2-Colr at 444 K, and Colr-I (isotropic liquid) at 564 K, where a fluidic discotic rectangular columnar (Colr) liquid crystal phase was observed in a wide temperature range of 444-564 K before melting. The one-dimensional columnar molecular assembly of (1)∞ was constructed using a simultaneous operation of N-H···O= hydrogen-bonding and π-stacking interactions. Temperature (T)- and frequency (f)-dependent dielectric constants of 1 indicated characteristic dielectric enhancement at higher-T and lower-f conditions above 500 K because of the thermally activated motional freedom of the polar N-H···O= hydrogen-bonding unit in the Colr phase. The polarization-electric field (P-E) curves at f = 0.1 Hz clearly indicated ferroelectric hysteresis behavior with a remanent polarization (Pr) of 1 μC cm-2 and a coercive electric field (Ec) of 2 V μm-1 at 503 K. The stable operation of the high-T ferroelectrics at approximately 500 K facilitates the potential application of a memory device in a high-T environment.

    DOI: 10.1021/acs.jpcc.9b03866

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  • Ferroelectric Behavior of a Hexamethylenetetramine-Based Molecular Perovskite Structure 査読

    Hagino Morita, Ryo Tsunashima, Sadafumi Nishihara, Katsuya Inoue, Yuriko Omura, Yasutaka Suzuki, Jun Kawamata, Norihisa Hoshino, Tomoyuki Akutagawa

    Angewandte Chemie - International Edition   58 ( 27 )   9184 - 9187   2019年7月

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    掲載種別:研究論文(学術雑誌)  

    We report the development of a molecular ferroelectric material inspired by the hexamethylenetetramine (hmta) non-centrosymmetric molecular rotator. The bromide salt of diprotonated hmta (hmtaH2) crystalized as (hmtaH2)(NH4)Br3 in a metal-free ABX3 perovskite-type structure, in which the A and B sites are occupied by hmtaH22+ and ammonium cations, respectively. The compound crystallized in the Pma2 polar space group. A distorted polar perovskite structure formed owing to the distortion of {(NH4)Br6} octahedrons that are stabilized through the formation of NH⋅⋅⋅Br hydrogen bonds and the orientational ordering of positive charges on the non-centrosymmetric hmtaH2 molecules. This spontaneous polarization exhibited ferroelectric behavior with a nominally high Curie temperature (>400 K), in which the electrical switching of polarization originates from the rotation of the hmtaH2 unit.

    DOI: 10.1002/anie.201905087

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  • High Thermally Stable n-Type Semiconductor up to 850 K Based on Dianionic Naphthalenediimide Derivative 査読

    Ayumi Kawasaki, Takashi Takeda, Norihisa Hoshino, Wakana Matsuda, Shu Seki, Tomoyuki Akutagawa

    Journal of Physical Chemistry C   123 ( 25 )   15451 - 15457   2019年6月

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    掲載種別:研究論文(学術雑誌)  

    Electrostatic cation-anion interaction is effective to form a tightly bounded π-molecular assembly, which enhances the thermal stability and carrier transport property. Dianionic bis(benzenesulfonate)-naphthalenediimide (BSNDI2-) formed simple 2:1 cation-anion pairs of (Na+)2(BSNDI2-) (1), (K+)2(BSNDI2-) (2), and (NH4+)2(BSNDI2-) (3), and their redox behaviors, thermal stabilities, crystal structures, electron transport properties, and dielectric constants were compared to those of neutral bis(phenyl)-naphthalenediimide (4). Crystals 1, 2, and 3 had quite high thermal stabilities up to 850, 810, and 600 K, respectively, even though organic molecules. A two-dimensional (2D) n-type electron transport layer consisting of NDI πcores was sandwiched between networks of highly polarized electrostatic cation-anion pairs showing 2D herringbone (1), one-dimensional π-stacking (2), and brickstone-like 2D π-stacking (3) interactions. The values of electron mobility in polycrystalline 1, 2, 3, and 4 reached 0.22, >0.0003, 0.036, and >0.028 cm2 V-1 s-1, respectively, according to flash-photolysis time-resolved microwave conductivity measurements. The electron mobility of crystal 1 was 1 order of magnitude higher than those of crystals 2, 3, and 4 owing to the tight intermolecular interactions within the 2D transport layer. The real part dielectric constants of crystals 1, 2, 3, and 4 were ∼4, ∼50, ∼20, and ∼4 at 450 K, respectively, which affected the electron transport property. The chemical design of highly polarized electrostatic cation-anion pair formed the 2D transport layer and also has high thermal stability up to ∼850 K in the ionic n-type semiconducting materials.

    DOI: 10.1021/acs.jpcc.9b03023

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  • Reversible Channel-Layer Structural Transformation of a Hydrogen-Bonded Bis-Urea Macrocycle 査読

    Guohao Yuan, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    Crystal Growth and Design   19 ( 6 )   3509 - 3517   2019年6月

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    掲載種別:研究論文(学術雑誌)  

    Bis-urea macrocycle 1 forms N-H···O= hydrogen-bonded one-dimensional (1D) channels, and the acetic acid (AcOH) dimer can be introduced into the 1D tubular channels, forming a 1D guest adsorption crystal (S1). The guest AcOH was easily desorped from the 1D channel to generate an empty 1D channel (S1′), which was further transformed into a thermodynamically stable two-dimensional (2D) hydrogen-bonding zigzag layer (S2) at temperatures above 520 K. The formation of host-guest molecular complexes with 1-dichloroacetic acid, tetrahydrofuran, pyrrole, pyridine, 3,4-difluoroaniline, and 1,4-diaminoalkanes was confirmed by X-ray crystal structural analyses, and molecular assembly structures of isolated monomers (S0), 1D channels (S1), 2D layers (S2), and dimeric 2D layers (S3), respectively, were observed depending on the size and shape of guest molecules. Guest desorption from the S0, S1, S2, and S3 assemblies resulted in a structural transformation to the thermodynamically stable guest-free S2′. Of these structures, a transformation from 1D guest-filled channel S1 to guest-free S1′ was observed for linear guests of (AcOH)2 dimers and NH2(CH2)nNH2 (n = 3, 5, and 7) with a molecular length longer than ca. 1 nm. The guest-filled 2D layer of S2 was transformed to S2′ after the guest desorption and also to S1 through AcOH readsorption, suggesting a reversible S1-S2′ structural transformation by stepwise thermal treatment and guest adsorption-desorption processes. Both the N2 and CO2 adsorption behaviors were not observed in thermodynamically stable S2′, whereas selective CO2 adsorption was confirmed in S1′.

    DOI: 10.1021/acs.cgd.9b00370

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  • Hydrogen-Bonded Polyrotaxane Cation Structure in Nickel Dithiolate Anion Radical Salts: Ferromagnetic and Semiconducting Behavior Associated with Structural Phase Transition 査読

    Yuki Shirakawa, Kiyonori Takahashi, Hiroyasu Sato, Norihisa Hoshino, Hayato Anetai, Shin ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura

    Chemistry - A European Journal   25 ( 28 )   6920 - 6927   2019年5月

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    掲載種別:研究論文(学術雑誌)  

    The pseudo-polyrotaxane structure of [(H-bpy + )- (DB-24-crown-8)] ∞ (H-bpy + = monoprotonated 4,4-bipyridinium; DB-24-crown-8 = dibenzo-24-crown-8) has been incorporated into the anion radical salt [Ni(dmit) 2 ] − (dmit 2− = 1,3-dithiole-2-thione-4,5-dithiolate). (H-bpy + )(DB-24-crown-8)[Ni(dmit) 2 ] − crystallized as two polymorphs, crystals 1 and 2. Crystal 1 was found to have a lower density and looser packing structure in which H-bpy + forms a one-dimensional hydrogen-bonding chain that passes though the crown ether ring of DB-24-crown-8. DB-24-crown-8 adopts a U-shaped conformation in which two phenylene rings sandwich one of the pyridyl rings of H-bpy + to stabilize the structure. The [Ni(dmit) 2 ] − anions are arranged in a layer parallel to the (10) plane with uniform side-by-side interactions. A structural phase transition was observed at 235 K, accompanied by ordering of the polyrotaxane structure. In crystal 1, at 173 K, H-bpy + is twisted around the central C−C bond, which perturbs the arrangement of [Ni(dmit) 2 ] − through short C−H⋅⋅⋅S contacts. As a result, the semiconducting behavior, with an activation energy of 0.21 eV, becomes insulating below 235 K. The crystal exhibits ferromagnetic interactions because of the weak side-by-side interactions between [Ni(dmit) 2 ] − anions. Crystal 2 has a similar pseudo-polyrotaxane structure but showed no phase transition. This suggests that the looser crystal packing in crystal 1 induces the structural change of the pseudo-polyrotaxane, perturbing the electron system of [Ni(dmit) 2 ] − .

    DOI: 10.1002/chem.201806230

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  • Ferroelectric Alkylamide-Substituted Helicene Derivative with Two-Dimensional Hydrogen-Bonding Lamellar Phase 査読

    Hayato Anetai, Takashi Takeda, Norihisa Hoshino, Higashi Kobayashi, Nozomi Saito, Masanori Shigeno, Masahiko Yamaguchi, Tomoyuki Akutagawa

    Journal of the American Chemical Society   141 ( 6 )   2391 - 2397   2019年2月

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    掲載種別:研究論文(学術雑誌)  

    Alkylamide (-CONHC n H 2n+1 )-substituted benzene and its pyrene derivatives have shown a discotic hexagonal columnar liquid-crystalline phase through a one-dimensional (1D) intermolecular N-H···O hydrogen-bonding interaction, the direction of which is inverted through the application of an alternate current voltage. The polar hydrogen-bonding chains and dipole inversion reveal a ferroelectric polarization-electric field (P-E) hysteresis curve. Non-planar helicene derivatives bearing two CONHC 14 H 29 chains also indicate a ferroelectric response. The racemic helicene derivative shows a bilayer lamellar liquid-crystal phase within a temperature range of 330-420 K, whereas there is no liquid crystallinity for the optically active derivative because of the different molecular assembly structure. The racemic phase is constructed through a two-dimensional (2D) N-H···O hydrogen-bonding network, which shows ferroelectric P-E hysteresis curves at above 340 K. The collective dipole inversion in the 2D layer contributes to the ferroelectricity in the lamellar phase. The remanent polarization (P r ) of 11.1 μC cm -2 is about 6 times higher than those of the planar benzene- and pyrene-based 1D ferroelectrics. Both the density of the hydrogen-bonding site and the domain orientation in the 2D system are higher than those of the 1D columnar system.

    DOI: 10.1021/jacs.8b11222

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  • Heat-Triggered Crystallization of Liquid Crystalline Macrocycles Allowing for Conductance Switching through Hysteretic Thermal Phase Transitions 査読

    Takahiro Muraoka, Tatsuya Shima, Takashi Kajitani, Norihisa Hoshino, Estelle Morvan, Axelle Grélard, Erick J. Dufourc, Takanori Fukushima, Tomoyuki Akutagawa, Kota Nabeya, Kazushi Kinbara

    Chemistry - An Asian Journal   14 ( 1 )   141 - 148   2019年1月

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    掲載種別:研究論文(学術雑誌)  

    A polymesomorphic thermal phase-transition of a macrocyclic amphiphile consisting of aromatic groups and oligoethylene glycol (OEG) chains is reported. The macrocyclic amphiphile exists in a highly-ordered liquid crystal (LC) phase at room temperature. Upon heating, this macrocycle shows phase-transition from columnar-lamellar to nematic LC phases followed by crystallization before melting. Spectroscopic studies suggest that the thermally induced crystallization is triggered by a conformational change at the OEG chains. Interestingly, while the macrocycle returns to the columnar-lamellar phase after cooling from the isotropic liquid, it retains the crystallinity after cooling from the thermally-induced crystal. Thanks to this bistability, conductance switching was successfully demonstrated. A different macrocyclic amphiphile also shows an analogous phase-transition behavior, suggesting that this molecular design is universal for developing switchable and memorizable materials, by means of hysteretic phase-transition processes.

    DOI: 10.1002/asia.201801372

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  • Dielectric and Sorption Responses of Hydrogen-Bonding Network of Amorphous C<sub>60</sub>(OH)<sub>12</sub> and C<sub>60</sub>(OH)<sub>36</sub> 査読

    Shota Uchikawa, Ayumi Kawasaki, Norihisa Hoshino, Takashi Takeda, Shin Ichiro Noro, Kiyonori Takahashi, Takayoshi Nakamura, Nozomi Sato, Ken Kokubo, Hidehiro Sakurai, Tomoyuki Akutagawa

    Journal of Physical Chemistry C   2019年

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    掲載種別:研究論文(学術雑誌)  

    Hydrophilic fullerene derivatives of C60(OH)12 (1) and C60(OH)36 (2) bearing different numbers of -OH groups formed amorphous solids of 1·x(H2O) (x = 5-10) and 2·x(H2O) (x = 15-22), respectively, according to the humidity. The thermally activated dynamic molecular motion of polar H2O was confirmed in the DSC and dielectric spectra. Three-dimensional O-H···O hydrogen-bonding networks in amorphous 1 and 2 produced extrinsic adsorption-desorption pores with a hydrophilic environment posed by -OH groups, where N2, CO2, H2, and CH4 gases vapors and polar H2O, MeOH, and EtOH molecules reversibly adsorbed into the networks. The molecular motion of polar H2O was directly observed in dielectric enhancement and protonic conductivity in three-dimensional O-H···O hydrogen-bonding networks. The Brunauer-Emmett-Teller (BET) specific surface areas of amorphous 1 and 2 were 315 and 351 m2 g-1, respectively, from the CO2 sorption isotherms. Reversible vapor sorption behaviors with structural changes of amorphous 1 and 2 were also confirmed for the polar H2O, MeOH, and EtOH.

    DOI: 10.1021/acs.jpcc.9b06951

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  • The trinuclear platinum(ii) complex in Vèzes' red salt as a building block of coordination polymers 査読

    Norihisa Hoshino, Sena Fujita, Tomoyuki Akutagawa

    Dalton Transactions   48 ( 1 )   176 - 181   2019年

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    掲載種別:研究論文(学術雑誌)  

    One-dimensional (1D) and three-dimensional (3D) coordination polymers comprising triangular [Pt 3 (NO 2 ) 6 (μ 3 -O)] 2− ([Pt3] 2− ) units were prepared from K 2 [Pt3]·3H 2 O (1), also known as Vèzes' red salt. The reaction between 1 and excess 18-crown-6 ether afforded the 1D coordination polymer [K(18-crown-6)] 2 [Pt3] (2), whereas the reaction between 1, excess 18-crown-6 ether, and AgPF 6 afforded the 1D coordination polymer [Ag(18-crown-6)] 2 [Pt3]·(CH 3 ) 2 CO (3). However, the reaction between 1 and equimolar amounts of 18-crown-6 and AgPF 6 afforded the 3D coordination polymer [Ag 2 (18-crown-6)][Pt3]·(CH 3 ) 2 CO (4). Furthermore, the 3D coordination polymer [Ag 2 Pt 3 (μ 3 -O)(NO 2 ) 6 ((CH 3 ) 2 CO) 2 ]·(CH 3 ) 2 CO (5) containing three Pt 2+ → Ag + dative bonds was obtained by the reaction of 1, Bu 4 NPF 6 , and AgPF 6 . The N 2 , O 2 , and CO 2 gas absorption isotherms of 1-5 were obtained, revealing that the dry crystals of 4 exhibit a selective CO 2 absorption ability.

    DOI: 10.1039/c8dt04121k

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  • Nanoscale Effects in One-Dimensional Columnar Supramolecular Ferroelectrics 査読

    Hayato Anetai, Kohei Sambe, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    Chemistry - A European Journal   25 ( 48 )   11233 - 11239   2019年

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    掲載種別:研究論文(学術雑誌)  

    Organic ferroelectrics have been actively developed with the goal of fabricating environmentally friendly and low-cost memory devices. The remanent polarization of hydrogen-bonded organic ferroelectrics approaches that of the inorganic ones. Nanoscale fabrication of organic ferroelectrics is an essential aspect of high-density memory devices. A pyrene derivative with four tetradecylamide (−CONHC14H29) chains (1) formed an amide-type N−H⋅⋅⋅O hydrogen-bonded one-dimensional (1D) column, which demonstrated ferroelectricity in the discotic hexagonal columnar (Colh) liquid crystalline phase through the inversion of the orientation of the hydrogen-bonded chains. On the contrary, similar chiral pyrene derivatives bearing 3,7-dimethyl-1-octhylamide chains (S-2 and R-2) did not indicate the Colh phase and ferroelectricity. Homogeneous mixed liquid crystals (1)1−x(S-2)x (i.e., between the ferroelectric 1 and the non-ferroelectric S-2) enable the control of the nanoscale aggregation state of the organic ferroelectrics, resulting in a nanoscale effect of the 1D supramolecular ferroelectrics. Ferroelectric mixed liquid crystals (1)1−x(S-2)x were observed at x≦0.03, where one S-2 molecule was inserted after every thirty-three 1 molecule in the mixed liquid crystal (1)33(S-2). An average (1)34 length of approximately 12 nm was required to maintain the 1D ferroelectricity, which was similar to the nanoscale limit of inorganic ferroelectrics, such as hafnium oxide thin film (≈15 nm).

    DOI: 10.1002/chem.201902544

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  • One-dimensional single-helix coordination polymer self-assembled by a crown-ether appended-N-heteroacene radical anion 査読

    Kyosuke Isoda, Hinako Takahashi, Yuichiro Mutoh, Norihisa Hoshino, Tomoyuki Akutagawa

    Dalton Transactions   48 ( 35 )   13125 - 13129   2019年

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    掲載種別:研究論文(学術雑誌)  

    A crown-ether appended N-heteroacene 1 was reduced in the presence of NaBPh4 to the radical anion 2 by accepting one electron transferred from both the cathode and BPh4- as a reductant. The obtained radical anion 2 can function as a radical anion ligand to bridge two sodium ions to self-assemble into one-dimensional helical coordination polymers.

    DOI: 10.1039/c9dt02797a

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  • Intermolecular interactions of tetrabenzoporphyrin- And phthalocyanine-based charge-transfer complexes 査読

    Miki Nishi, Yuki Hayata, Norihisa Hoshino, Noriaki Hanasaki, Tomoyuki Akutagawa, Masaki Matsuda

    Dalton Transactions   48 ( 48 )   17723 - 17728   2019年

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    掲載種別:研究論文(学術雑誌)  

    The effect of molecular modification on the intermolecular interactions in tetrabenzoporphyrin-based charge transfer complexes is reported. TPP[FeIII(tbp)Cl2]2, TPP[CoIII(tbp)Cl2]2 and TPP[CoIII(tbp)Br2]2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) were synthesized and their crystal structures were compared to those of the reported TPP[MIII(tbp)(CN)2]2, TPP[FeIII(tbp)Br2]2 and TPP[MIII(Pc)L2]2 complexes (Pc = phthalocyanine; and L = CN, Cl or Br). The prepared CT complexes were isostructural to reported systems. However, their intermolecular interactions were found to depend on the combination of the macrocyclic (Mc) and axial ligands (L). In Pc-based systems, the overlap integral between HOMOs of Pc decreased with the increase in the size of the axial ligand, which indicated that the intermolecular interactions in Pc-based systems were dominated by repulsive interactions. On the other hand, in tbp-based systems, attractive and repulsive interactions competed with each other. Furthermore, charge transport properties were found to depend on the central metal ion as well as the combination of Mc and L, which suggested that minor molecular modifications to porphyrin complexes will cause drastic changes in both inter- and intramolecular interactions.

    DOI: 10.1039/c9dt03653a

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  • A Trinuclear Iron(III) Complex of a Triple Noninnocent Ligand for Spin-Structured Molecular Conductors 査読

    Norihisa Hoshino, Tomoyuki Akutagawa

    Chemistry - A European Journal   24 ( 72 )   19323 - 19331   2018年12月

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    掲載種別:研究論文(学術雑誌)  

    N,N′,N′′,N′′′,N′′′′,N′′′′′-(Triphenylene-2,3,6,7,10,11-hexayl)hexapicolinamide (H6hptp), a triangular ligand containing three noninnocent coordination sites, and its trinuclear iron(III) complex (PPh4)3[FeIII3(hptp)6(CN)6] were prepared. In this complex, three low-spin Fe3+ ions are coordinated by the triangular hptp6− bridging ligand at its apices. Cyclic voltammetry of (PPh4)3[FeIII3(hptp)6(CN)6] in PhCN solution showed one reductive wave for 3 Fe2+/3 Fe3+ and three oxidative waves for the hptp6− ligand. The controlled-potential electronic spectra of the solution presented broad absorption bands in the near-IR (NIR) region for oxidations because a π-radical is generated on the hptp6− ligand. The EPR spectra of frozen solutions also showed large oxidization-state dependent differences caused by the strong exchange interactions between the electrons in the d orbitals of the Fe3+ ions and those of the π-radicals in the hptp6− ligand. The electronic and magnetic states of the oxidized species were investigated using density functional theory.

    DOI: 10.1002/chem.201804280

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  • Molecular assemblies of tetrahedral triphenylmethanol and triphenylamine derivatives bearing −NHCOC <sub>N</sub> H <sub>2</sub> n <sub>+1</sub> chains 査読

    Satoru Akahane, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    Crystal Growth and Design   18 ( 10 )   6284 - 6292   2018年10月

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    掲載種別:研究論文(学術雑誌)  

    Nonplanar three-fold symmetrical triphenylmethanol (1: n = 10 and 2: n = 3) and triphenylamine (3: n = 10 and 4: n = 3) derivatives bearing three alkylamide (−NHCOC n H 2 n +1 ) chains were studied in terms of their phase transitions, molecular assemblies, nano- or meso-structures, and dielectric responses. Slight modification of the structural core from a hydroxyl moiety (C−OH in 1) to a nitrogen atom (N in 3) drastically changed the molecular assembly structures and physical properties in solids. The molecular assembly of 1 showed a glass−plastic crystal phase transition at ∼340 K, whereas 3 only displayed a direct solid−liquid phase transition. Uniform microscale spheres and nanowires with average diameters of 2 μm and 200 nm, respectively, were observed for the molecular assemblies of 1 and 3 on substrate surfaces, respectively, corresponding to amorphous glass and one-dimensional hydrogen-bonding columnar structures. An α-type frequency- and temperature-dependent dielectric relaxation was observed in amorphous 1 during the glass−plastic crystal phase transition, whereas no dielectric anomalies were observed for 3. This difference was attributed to the subtle chemical modification of the central core from C−OH to N.

    DOI: 10.1021/acs.cgd.8b01152

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  • Molecular Structure of the Photo-Oxidation Product of Ellagic Acid in Solution 査読

    Hisashi Tokutomi, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    ACS Omega   3 ( 9 )   11179 - 11183   2018年9月

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    掲載種別:研究論文(学術雑誌)  

    The photoreaction of the antioxidant ellagic acid (EA) elicits a drastic coloration in solution from colorless to yellow in aerated tetrahydrofuran, which appears as a new absorption band at 405 nm. Analysis of the X-ray crystal structure suggests that the photo-oxidation product of EA is a multiple cleavage π-structure (Ox-EA) that results from the interaction of EA with singlet oxygen followed by sequential cleavage and rearrangement steps.

    DOI: 10.1021/acsomega.8b01716

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  • Dynamic Motion of Organic Ligands in Polar Layered Cobalt Phosphonates 査読

    Zhong Sheng Cai, Norihisa Hoshino, Song Song Bao, Jiage Jia, Tomoyuki Akutagawa, Li Min Zheng

    Chemistry - A European Journal   24 ( 51 )   13495 - 13503   2018年9月

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    掲載種別:研究論文(学術雑誌)  

    By introducing the polar methoxy group into phenyl- or benzyl-phosphonate ligands, four cobalt phosphonates with layered structures are obtained, namely, [Co(4-mopp)(H2O)] (1), [Co(4-mobp)(H2O)] (2), [Co(3-mopp)(H2O)] (3), and [Co(3-mobp)(H2O)] (4), where 4- or 3-moppH2 is (4- or 3-methoxyphenyl)phosphonic acid and 4- or 3-mobpH2 is (4- or 3-methoxybenzyl)phosphonic acid. Compounds 1, 2, and 4 crystallize in the polar space groups Pmn21 or Pna21, whereas compound 3 crystallizes in the centrosymmetric space group P21/n. The layer topologies in the four structures are similar and can be viewed as perovskite type, where the edge-sharing [Co4O4] rhombi are capped by the PO3C groups. The phenyl and MeO groups in compounds 1–3 are heavily disordered, whereas that in 4 is ordered. Structural comparison based on the data at 296 and 123 K reveals distinct dynamic motion of the organic groups in compounds 1 and 2. The fluctuation of the polar MeO groups in these two compounds is confirmed by dielectric relaxation measurements. In contrast, the fluctuation of polar groups in compounds 3 and 4 is not evident. Interestingly, the dehydrated samples of 3 and 4 (i.e., 3-de and 4-de) exhibit one-step and two-step phase transitions associated with the motion of polar organic groups, as proven by DSC and dielectric measurements. The magnetic properties of compounds 1–4 are investigated, and strong antiferromagnetic interactions are found to mediate between the magnetic centers through μ-O(P) and O-P-O bridges.

    DOI: 10.1002/chem.201801301

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  • ESIPT Fluorescent Chromism and Conformational Change of 3-(2-Benzothiazolyl)-4-hydroxy-benzenesulfonic acid by Amine Sorption 査読

    Yuta Nakane, Takashi Takeda, Norihisa Hoshino, Ken Ichi Sakai, Tomoyuki Akutagawa

    Journal of Physical Chemistry C   122 ( 28 )   16249 - 16255   2018年7月

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    掲載種別:研究論文(学術雑誌)  

    Sulfonic acid (-SO3H)-substituted 2-(2′-hydroxyphenyl)benzothiazole (1) was designed as a new solid-state ESIPT (excited-state intramolecular proton transfer) fluorescent chromic molecule that responds to various types of organic bases and amines as a sensing device of biologically important molecules such as ammonia and histamine. Crystal 1 exhibited a reversible adsorption-desorption behavior with pyridine, aniline, thiazole, quinoline, ammonia, propylamine, octylamine, diethylamine, 1,4-diaminobutane, histamine, and other compounds. The sorption behavior of these compounds induced the fluorescent chromism of crystal 1 from non-ESIPT weak blue, to ESIPT strong green, and finally to non-ESIPT strong green emissions, which applied to the solid-state sensing devices for biologically important organic bases and amines.

    DOI: 10.1021/acs.jpcc.8b03248

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  • Circular Polarized Luminescence of Hydrogen-Bonded Molecular Assemblies of Chiral Pyrene Derivatives 査読

    Hayato Anetai, Takashi Takeda, Norihisa Hoshino, Yasuyuki Araki, Takehiko Wada, Shunsuke Yamamoto, Masaya Mitsuishi, Hiromu Tsuchida, Tomoki Ogoshi, Tomoyuki Akutagawa

    Journal of Physical Chemistry C   122 ( 11 )   6323 - 6331   2018年3月

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    掲載種別:研究論文(学術雑誌)  

    The absorption and fluorescence spectra of chiral alkylamide-substituted pyrene derivatives (R-1 and S-1) in the solution phase were consistent with the formation of N-H···Oâ• hydrogen-bonded helical π-stacked one-dimensional (1D) supramolecules (R-1)n and (S-1)n in methylcyclohexane (MCH), toluene, chloroform (CHCl3), and tetrahydrofuran (THF); the π-stacked structures and aggregation number (n) were governed by the concentration (c) and solvent polarity. The aggregation of (R-1)n and (S-1)n in MCH and toluene was much greater than that in THF and CHCl3, and excimer emission of excited-state (R-1)n∗ and (S-1)n∗ supramolecules with n ≥ 2 was observed in all solvents. Interestingly, the circular polarized luminescence (CPL) spectra of (R-1)n∗ and (S-1)n∗ revealed a glum value of 0.03 in MCH at c > 1 × 10-6 M. Circular dichroism and CPL spectra revealed the formation of hydrogen-bonded helical 1D supramolecular assemblies in the ground and excited states. The helicities of the 1D supramolecular assemblies of (R-1)n and (S-1)n in CHCl3 were inverted as compared to those in MCH and THF. The solvent polarity and concentration were sensitive to the π-stacked structure and helical configuration of the N-H···Oâ• hydrogen-bonded 1D supramolecular assemblies.

    DOI: 10.1021/acs.jpcc.7b12747

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  • Host-Guest Molecular Crystals of Diamino-4,4-bithiazole and Dynamic Molecular Motions via Guest Sorption 査読

    Hiroshi Nishiyama, Takashi Takeda, Norihisa Hoshino, Kiyonori Takahashi, Shin Ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa

    Crystal Growth and Design   18 ( 1 )   286 - 296   2018年1月

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    掲載種別:研究論文(学術雑誌)  

    Diamino-4,4-bithiazole (1) formed host-guest binary molecular crystals with various types of organic guest molecules including pyridine (Py), benzonitrile (PhCN), piperidine (Pipe), DMF, THF, 1,4-dioxane (Diox), CH3OH, aniline (Ani), coumarin (Coum), nitrobenzene (PhNO2), hexamethylenetetramine (HMTA), and quinoline (Quino). Single crystal X-ray structural analyses at 100 K revealed the formation of 1·(guest) or 1·(guest)2 crystals. Reversible molecular adsorption-desorption responses were observed with Py, PhCN, Pipe, DMF, and Diox around room temperature as the crystalline powders were heated during the desorption process and exposed to guest vapor during the readsorption process. The adsorption-desorption isotherms of crystalline powders 1 with Diox at 298 K indicated a reversible gate-opening adsorption-desorption process. Although the host-guest molecular crystals 1·(THF)2 and 1·(CH3OH)2 were confirmed by X-ray crystal structural analyses at 100 K, the THF and CH3OH guests were already eliminated at room temperature. Guest desorption processes of crystalline powders 1·(guest)x were not observed in the host-guest molecular crystals with Ani, Coum, PhNO2, HMTA, and Quino after the crystalline powders were heated. A balance of both the dipole moment and vapor pressure of the guest molecules played an essential role to elicit reversible guest sorption. The crystal structures formed on account of double N-H⋯N hydrogen-bonded one-dimensional (1D) chains between the -NH2 group and the ring nitrogen atom of 1, which interacted to form two-dimensional (2D) sheet structures through π-stacking and/or S⋯S interactions. Alternating layers of N-H⋯N hydrogen-bonded herringbone packing of 1 and the guest molecules led to the formation of other types of crystal lattices. The hydrogen-bonding molecular assemblies of 1 demonstrated lattice flexibly via the configuration change in the molecular arrangements according to the boiling point of the guest molecules.

    DOI: 10.1021/acs.cgd.7b01236

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  • Thermal and optical properties of multiblock macrocycles with hysteretic polymorphic transitionf 査読

    Kota Nabeya, Takahiro Muraoka, Norihisa Hoshino, Miho Aizawa, Takashi Kajitani, Tomoyuki Akutagawa, Atsushi Shishido, Takanori Fukushima, Kazushi Kinbara

    Materials Chemistry Frontiers   2 ( 5 )   969 - 974   2018年

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    掲載種別:研究論文(学術雑誌)  

    The thermal phase transition properties of macrocyclic molecules 1 and 2 consisting of aromatic 1,4-bis(phenylethynyl)benzene (BPEB) components and tetraethylene glycol (TEG) chains were investigated. 1 and 2 are structural isomers with a small difference at the connecting points of the BPEB units with TEG chains, where 1 has a lower structural symmetry than 2. 1 forms a crystal Cr1 upon cooling from the isotropic liquid. 1 at Cr1 shows a crystal-to-crystal polymorphic transition upon heating affording Cr2. Since the Cr1-to-Cr2 phase transition of 1 is an exothermic process, Cr2 is considered to be thermodynamically more stable than Cr1. Indeed, cooling from Cr2 shows no phase transition, and this hysteretic polymorphic transition allows the preparation of 1 in different crystalline states, namely Cr1 and Cr2, at room temperature. In contrast, 2 shows a reversible transition between a crystal and a nematic phase upon temperature changes. Based on the polymorphism of 1, switching of an optical property as a memory function is also demonstrated. Thus, the molecular structure of 1 with a lower structural symmetry than that of 2 is likely an important factor for the crystallization and its thermoresponsive polymorphic phase transition property.

    DOI: 10.1039/c7qm00621g

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  • Tubular and lamellar hydrogen-bonding molecular assemblies of isophthalic acid derivatives bearing a -CONHC<sub>n</sub>H<sub>2 n +1</sub> chain 査読

    Chao Lv, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    RSC Advances   8 ( 39 )   22250 - 22258   2018年

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    掲載種別:研究論文(学術雑誌)  

    Isophthalic acid derivatives (CnIP), bearing alkylamide chains (-CONHCnH2n+1: n = 6, 10, 14, and 18) at the 5-position that can participate in hydrogen bonding, were prepared and evaluated for their hydrogen-bonding molecular assembly structures for organogelation and liquid crystal formation. The hydrogen-bonding carboxylic acid (-COOH) groups form a ring-shaped (CnIP)6 hexamer or a one-dimensional (1D) zig-zag (CnIP)∞ chain. Although neither organogelation nor liquid crystal formation was observed in the isophthalic acid derivative bearing an alkoxy (-OC14H29) chain, C14IP and C18IP derivatives could form both organogel and liquid crystal states through intermolecular N-H⋯O = amide-type hydrogen-bonding interactions. A discotic hexagonal columnar liquid crystal (Colh) phase was observed in hydrated (C14IP)6·(H2O)n and (C18IP)6·(H2O)n, whereas a lamella-type liquid crystal (La) phase was confirmed in the unhydrated C18IP. In the Colh phase, O-H⋯O hydrogen-bonding ring-shaped (C14IP)6 and (C18IP)6 hexamers assembled to form the tubular molecular assembly stabilized by intermolecular-N-H⋯O = hydrogen-bonding interactions along the tube growth direction, where H2O molecules were contained within the hydrophilic space. On the other hand, the N-H⋯O = hydrogen-bonding interactions between the 1D zig-zag (CnIP)∞ chains formed a layer-type molecular assembly of the La-phase in the absence of water molecules.

    DOI: 10.1039/c8ra04077j

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  • An electrically conducting crystal composed of an octahedrally ligated porphyrin complex with high-spin iron(III) 査読

    Miki Nishi, Ryuta Ishii, Mitsuo Ikeda, Noriaki Hanasaki, Norihisa Hoshino, Tomoyuki Akutagawa, Michinori Sumimoto, Masaki Matsuda

    Dalton Transactions   47 ( 12 )   4070 - 4075   2018年

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    掲載種別:研究論文(学術雑誌)  

    A porphyrin-based octahedrally ligated complex with high-spin iron(iii) was designed, and the resulting electrically conducting crystal TPP[FeIII(tbp)Br2]2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) was synthesised. Although TPP[Fe(tbp)Br2]2 was isostructural to the reported TPP[Fe(Mc)L2]2 systems (Mc = macrocyclic ligands such as phthalocyanine (Pc) or tbp; and L = CN, Cl, or Br), the bond lengths between Fe and ligands in the [Fe(tbp)Br2] unit were evidently longer than those in the other units, because of the different spin states of Fe: high-spin in TPP[Fe(tbp)Br2]2 and low-spin in others. The magnetic anisotropy observed in the low-spin state vanished when the Fe is in the high-spin state. Based on reports for Pc-based systems, the negative magnetoresistance (MR) effect for TPP[Fe(tbp)Br2]2 was expected to be smaller than that for TPP[Fe(tbp)(CN)2]2. However, the former showed a giant negative MR effect similar to or larger than the latter, suggesting that the nature of iron is a crucial factor for the electrical properties of porphyrin-based materials.

    DOI: 10.1039/c7dt04649a

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  • Phase transition and molecular assembly structure of ellagic acid ester derivatives 査読

    Hisashi Tokutomi, Jianyun Wu, Takashi Takeda, Norihisa Hoshino, Tomoyuki Akutagawa

    New Journal of Chemistry   42 ( 18 )   14700 - 14703   2018年

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    掲載種別:研究論文(学術雑誌)  

    Ellagic acid and its esters (-OCOCnH2n+1) were examined in terms of phase transition, electronic structure, dielectric constant, and molecular assembly. The alternating layer arrangement of the one-dimensional π-stack and hydrophobic alkyl chains were observed in ellagic acid esters, and the in-plane amorphous glass state was observed at an optically isotropic assembly.

    DOI: 10.1039/c8nj02609b

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  • Synthesis of ordered carbonaceous frameworks from organic crystals 査読

    Hirotomo Nishihara, Tetsuya Hirota, Kenta Matsuura, Mao Ohwada, Norihisa Hoshino, Tomoyuki Akutagawa, Takeshi Higuchi, Hiroshi Jinnai, Yoshitaka Koseki, Hitoshi Kasai, Yoshiaki Matsuo, Jun Maruyama, Yuichiro Hayasaka, Hisashi Konaka, Yasuhiro Yamada, Shingi Yamaguchi, Kazuhide Kamiya, Takuya Kamimura, Hirofumi Nobukuni, Fumito Tani

    Nature Communications   8 ( 1 )   109   2017年12月

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    掲載種別:研究論文(学術雑誌)  

    Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni-porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873-1073 K. In addition, the porphyrin's Ni-N4 unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks.

    DOI: 10.1038/s41467-017-00152-z

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  • N-type semiconducting behavior of copper octafluorophthalocyanine in an organic field-effect transistor 査読

    Akane Matumoto, Norihisa Hoshino, Tomoyuki Akutagawa, Masaki Matsuda

    Applied Sciences (Switzerland)   7 ( 11 )   2017年10月

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    掲載種別:研究論文(学術雑誌)  

    Based on the crystal structure analysis, the overlap integral between the frontier molecular orbitals of adjacent F8CuPcs in the one-dimensional chain is estimated: the overlap integral between the lowest unoccupied molecular orbitals is 5.4 × 10-3, which is larger than that in a typical n-type semiconducing material F16CuPc (2.1 × 10-3), whereas that between the highest occupied molecular orbitals is 2.9 × 10-4. Contrary to previous studies in air, we found that an organic field-effect transistor (OFET) composed of F8CuPc essentially shows clear n-type semiconducting behavior in vacuum.

    DOI: 10.3390/app7111111

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  • Dual fluorescent zwitterionic organogels of a quinoxalinone derivative using cation-anion detection keys 査読

    Yuta Nakane, Takashi Takeda, Norihisa Hoshino, Ken Ichi Sakai, Tomoyuki Akutagawa

    Journal of Materials Chemistry C   5 ( 25 )   6234 - 6242   2017年

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    掲載種別:研究論文(学術雑誌)  

    An [18]crown-6 unit was introduced into a cation-anion dual-ion-sensing quinoxalinone derivative (1) as a new fluorescent molecule for successive cation (K+) and anion (F- and CH3COO-) sensing in CH3CN. High anion-sensing abilities for F- and AcO- were observed at the hydrogen-bonded acidic N-H proton of the positively charged K+-capturing 1 at the [18]crown-6 site due to electrostatic cation-anion interactions. On the other hand, the acidic N-H proton of lactam tautomer 1 strongly recognized basic AcO- or F- anions via N-H⋯AcO- or F- hydrogen-bonding interactions, and further AcO- or F- additions facilitated the deprotonation reaction, forming anionic 1-. Anionic 1- showed a much higher K+-sensing ability at the [18]crown-6 site than neutral 1 through effective cation-anion electrostatic interactions. Interestingly, the electrostatically stabilized zwitterionic K+·1- formed fluorescent organogels in CH3CN, acetone, and THF; the organogels underwent reversible transformation between a blue fluorescent organogel and green fluorescent sol by the addition of trifluoroacetic acid (gel → sol) and trimethylamine (sol → gel). Both K+ and AcO- (or F-) ions acted as the key ions in the fluorescent organogel formation.

    DOI: 10.1039/c7tc01242j

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  • An antiferromagnetically coupled heterometal Cu<sub>6</sub>Fe wheel 査読

    Ryo Saiki, Norifumi Yoshida, Norihisa Hoshino, Graham N. Newton, Takuya Shiga, Hiroki Oshio

    Chemistry Letters   46 ( 8 )   1197 - 1199   2017年

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    掲載種別:研究論文(学術雑誌)  

    A heterometal Cu6Fe wheel molecule, [CuII6FeIII(HL)6(OH)2(OCH3)4](NO3)3·6H2O (1·6H2O) (H2L = 1-(2-pyridine)-3-(2-pyrrole)acetylacetone) was synthesized by the one-pot reaction of H2L with copper and iron sources. X-ray structural analysis reveals that the heptanuclear wheel cluster consists of a central Fe(III) ion surrounded by six Cu(II) ions, linked through methoxo- and hydroxo-bridges. Cryomagnetic studies indicate intramolecular antiferromagnetic interactions were operative.

    DOI: 10.1246/cl.170365

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  • Electronic and crystal structures of 1,2,3-triazole-fused p-benzoquinone derivatives 査読

    M. Sato, T. Takeda, N. Hoshino, T. Akutagawa

    CrystEngComm   19 ( 6 )   910 - 917   2017年

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    掲載種別:研究論文(学術雑誌)  

    The preparation and crystal structure analyses of 1,2,3-triazole fused p-benzoquinone derivatives were performed conventionally from electronically active tetraamino-p-benzoquinone (1). The redox behaviour and crystal structure of 1 were compared with those of chemically stable strong electron donor tetrakis(dimethylamino)-p-benzoquinone (3). The reaction of 1 with NaNO2 generated a diazonium salt, which reacted further to give residual amino groups of 1, forming bis(1,2,3-triazole)-p-benzoquinone (2) in high yield. Along with intramolecularly cyclized compound 2, novel π-extended dimeric product bis(1,2,3-triazole)-phenazinetetraone (4) was also generated in this reaction and isolated in charge-transfer complexes with perylene and coronene. The molecular structures of neutral 2, monoanionic 2−, and dianionic 22− were confirmed by single crystal X-ray structural analyses, where the acidic protons in 2 existed in the 2-position of the 1,2,3-triazole unit, whereas one proton in 2− was localized at the 1-position of the 1,2,3-triazole unit. The electron accepting ability of bis(1,2,3-triazole)-p-benzoquinone derivatives decreased in the order 2 > 2− > 22− due to electrostatic repulsive interactions in the anion radical and dianion state. Hydrogen-bonded new electron acceptor 4 was surrounded by four H2O molecules in the crystalline state, which formed an alternating donor-acceptor π-stacking interaction.

    DOI: 10.1039/C6CE02167K

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  • Solid-state structure and electronic states of hydrogen-bonded dimer of pyridyl-substituted tetrathiafulvalene salted with PF<sub>6</sub><sup>-</sup> 査読

    Tomoaki Kanetou, Ryo Tsunashima, Norihisa Hoshino, Tomoyuki Akutagawa

    RSC Advances   7 ( 11 )   6236 - 6241   2017年

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    掲載種別:研究論文(学術雑誌)  

    Hydrogen bonding was investigated in a newly prepared salt of pyridyl-substituted tetrathiafulvalene (TTFPy) that formed a dimer structure by hydrogen bonding and was salted with PF6- anions, namely, (TTFPy2H)PF6 (1). Structural analysis of the salt by single-crystal X-ray diffraction and temperature-dependent FTIR spectra and measurements of its electrical conductivity and dielectric properties were performed. Thermal fluctuations were investigated for protons between two TTFPy molecules. An anisotropic dielectric anomaly was observed owing to local proton transfer between two pyridyl moieties. This behavior was well explained by a model of Debye-type dipole relaxation. In addition, DFT calculations showed that the dipole originated from local proton transfer, but the dipole moment in a network of TTFPy⋯H+⋯TTFPy dimers was amplified by a factor of 2 owing to coupling with the electronic polarization of TTFPy moieties.

    DOI: 10.1039/c6ra27814k

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  • Studies on the Magnetic Ground State of a Spin Möbius Strip 査読

    Graham N. Newton, Norihisa Hoshino, Takuto Matsumoto, Takuya Shiga, Motohiro Nakano, Hiroyuki Nojiri, Wolfgang Wernsdorfer, Yuji Furukawa, Hiroki Oshio

    Chemistry - A European Journal   22 ( 40 )   14205 - 14212   2016年9月

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    掲載種別:研究論文(学術雑誌)  

    Here we report the synthesis, structure and detailed characterisation of three n-membered oxovanadium rings, Nan[(V=O)nNan(H2O)n(α, β, or γ-CD)2]⋅m H2O (n=6, 7, or 8), prepared by the reactions of (V=O)SO4⋅x H2O with α, β, or γ-cyclodextrins (CDs) and NaOH in water. Their alternating heterometallic vanadium/sodium cyclic core structures were sandwiched between two CD moieties such that O-Na-O groups separated the neighbouring vanadyl ions. Antiferromagnetic interactions between the S=1/2 vanadyl ions led to S=0 ground states for the even-membered rings, but to two quasi-degenerate S=1/2 states for the spin-frustrated heptanuclear cluster.

    DOI: 10.1002/chem.201602439

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  • Tunneling motion and antiferroelectric ordering of lithium cations trapped inside carbon cages 査読

    Shinobu Aoyagi, Akio Tokumitu, Kunihisa Sugimoto, Hiroshi Okada, Norihisa Hoshino, Tomoyuki Akutagawa

    Journal of the Physical Society of Japan   85 ( 9 )   2016年9月

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    掲載種別:研究論文(学術雑誌)  

    Dielectric and X-ray diffraction measurements of [Li@C60](PF6) single crystals reveal the motion of the Li+ cations inside the C60 cages at low temperature. An increase in the dielectric permittivity below 100 K is consistent with a combined tunneling and hopping motion of the Li+ cation between two positions inside the C60 cage. A phase transition accompanied by a decrease in the dielectric permittivity at TC = 24 K is explained by an antiferroelectric ordering of the Li+ cations. The Li+ ordering is caused by interactions among electric dipole moments formed between the Li+ cations inside and the PF6- anions outside the C60 cages. The electric dipole moments that are switched by the Li+ tunneling and interact with each other are potential qubits in a quantum computer using electric dipole moments.

    DOI: 10.7566/JPSJ.85.094605

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  • Successive Phase Transition, Dielectric Ordering, and Liquid Crystalline Behavior of Simple (Laurylammonium)(Phenyl Phosphates) Salts 査読

    Zhong Sheng Cai, Shota Uchikawa, Norihisa Hoshino, Takashi Takeda, Li Min Zheng, Shin Ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa

    Journal of Physical Chemistry B   120 ( 27 )   6761 - 6770   2016年7月

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    掲載種別:研究論文(学術雑誌)  

    Successive phase transitions of three kinds of simple 1:1 organic salts of laurylammonium (LA)-phenyl (3-pyridyl) phosphate derivative were examined in terms of thermal properties, single crystal X-ray structural analyses, powder X-ray diffractions, and dielectric responses, where the phosphate anion was chemically modified from phenylphosphate (1) and 3-pyridylphosphate (2) to m-fluorophosphate (3). All 1:1 simple organic salts showed the successive solid-solid and solid-smectic A (SmA) phase transition with high thermal stability. Isostructural alternate cation-anion layer was observed in LA-1 and LA-2, and the packing structure of LA-3 was different from those of the former salts. The L-shaped cation-anion conformation in the molecular assemblies was transformed to the rod-like conformation through the phase transition to SmA phase, where both conformations coexisted in the intermediate solid phase of LA-2 and LA-3. The DSC, PXRD, and dielectric responses of LA-2 showed the antiferroelectric-paraelectric phase transition couple with the flip-flop motion of 3-pyridyl ring along the long axis of the molecule. On the contrary, such molecular motion of the phenyl ring did not show the dielectric phase transition due to no dipole change during molecular rotation of phenyl ring. The motional freedom of m-fluorophenyl ring in LA-3 was completely suppressed by the steric hindrance from the neighboring anions in the absence of dielectric ordering.

    DOI: 10.1021/acs.jpcb.6b02213

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  • Conformational Transformations of (C<sub>12</sub>H<sub>25</sub>NH<sub>3</sub><sup>+</sup>)(Pyridinesulfonate) in the Solid State 査読

    Atsushi Funada, Shota Uchikawa, Norihisa Hoshino, Takashi Takeda, Tomoyuki Akutagawa

    Chemistry - An Asian Journal   11 ( 6 )   915 - 925   2016年3月

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    掲載種別:研究論文(学術雑誌)  

    The phase-transition behaviors, crystal structures, and dielectric properties of four kinds of simple 1:1 organic salts of (C12H25NH3+)(benzenesulfonate) and (C12H25NH3+)(pyridine sulfonates) were examined from the viewpoint of intermolecular hydrogen-bonding interactions and dynamic conformational transformation in molecular assemblies. Crystals of (C12H25NH3+)(benzenesulfonate) and (C12H25NH3+)(3-pyridinesulfonate) were isostructural and solid-solid and solid-liquid-crystal smectic A (SmA) phase transitions were observed. These two crystals formed rodlike cation-anion assemblies. However, the two salts, (C12H25NH3+)(2-pyridinesulfonate) and (C12H25NH3+)(4-pyridinesulfonate), formed largely bent L-shaped cation-anion conformations. Interesting conformational transformations from rodlike to L-shaped assemblies were observed in (C12H25NH3+)(2-pyridinesulfonate) and (C12H25NH3+)(3-pyridinesulfonate). Spare the rod: Dynamic conformational transformations from rodlike to L-shaped assemblies were observed in 1:1 simple organic salts.

    DOI: 10.1002/asia.201501442

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  • A giant negative magnetoresistance effect in an iron tetrabenzoporphyrin complex 査読

    Miki Nishi, Mitsuo Ikeda, Akinori Kanda, Noriaki Hanasaki, Norihisa Hoshino, Tomoyuki Akutagawa, Masaki Matsuda

    Dalton Transactions   45 ( 42 )   16604 - 16609   2016年

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    掲載種別:研究論文(学術雑誌)  

    By measuring the electrical resistivity in TPP[FeIII(tbp)(CN)2]2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) under the application of a static magnetic field, a giant negative magnetoresistance (MR) effect with high anisotropy is observed. More specifically, the MR ratio at 13 K under a field of 9 T perpendicular to the c axis is -70%, whereas the MR ratio under a field parallel to the c axis is -40%. Furthermore, electron spin resonance (ESR) measurements indicate large anisotropy in the principal g-values of d spin (S = 1/2) in the [FeIII(tbp)(CN)2] unit; the g1 value almost perpendicular to the tbp plane and the g2 and g3 values almost parallel to the tbp plane are 3.60, 1.24, and 0.39, respectively. It is revealed that the anisotropy in the MR effect arises from the anisotropy in the d spin, suggesting that the d spins in TPP[FeIII(tbp)(CN)2]2 affect the π-conduction electron via the intramolecular π-d interaction. The anisotropy and magnitude in the giant negative MR effect for TPP[FeIII(tbp)(CN)2]2 are smaller than the corresponding values for the isostructural phthalocyanine (Pc) analogue TPP[FeIII(Pc)(CN)2]2. This is consistent with the fact that the intermolecular antiferromagnetic d-d interaction in TPP[FeIII(tbp)(CN)2]2 (suggested by the Weiss temperature: Θ = -8.0 K) is weaker than that in TPP[FeIII(Pc)(CN)2]2 (Θ = -12.3 K). This indicates that the minor modification in coordination complexes can significantly affect the MR effect via tuning the intermolecular d-d interaction as well as the intermolecular π-π overlap.

    DOI: 10.1039/c6dt01911k

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  • The crystal design of polar one-dimensional hydrogen-bonded copper coordination complexes 査読

    Kiyonori Takahashi, Norihisa Hoshino, Takashi Takeda, Koichiro Satomi, Yasutaka Suzuki, Shin Ichiro Noro, Takayoshi Nakamura, Jun Kawamata, Tomoyuki Akutagawa

    Dalton Transactions   45 ( 8 )   3398 - 3406   2016年

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    掲載種別:研究論文(学術雑誌)  

    Polar crystals exhibiting second-order harmonic generation (SHG) were designed by adjusting the intermolecular interactions of mononuclear Cu(ii) complexes in which one H2O, two pyridines (py), and two p-substituted benzoate (p-RBA) ligands (R = F, Cl, Br, I, CH3, and OCH3) were coordinated to a Cu(ii) ion, forming a penta-coordinated asymmetric [Cu(ii)(p-RBA)2(py)2(H2O)] mononuclear structure with a permanent dipole moment along the direction of the Cu-OH2 coordination axis. Each asymmetric [Cu(ii)(p-RBA)2(py)2(H2O)] complex formed a polar one-dimensional hydrogen-bonded chain, [Cu(ii)(p-RBA)2(py)2(H2O)]∞, between the non-coordinated carboxylate oxygen atom of the p-RBA ligand and the hydrogen atom of the H2O molecule. The formation of a polar crystal depended on the arrangement of polar hydrogen-bonded chains; the parallel arrangement of each polar chain resulted in a polar crystal. The chemical design of the R group in the p-RBA ligand enabled tuning of the magnitude of the interchain interactions and crystal polarity; polar crystals were obtained using p-RBA ligands with R = Cl, Br, I, and OCH3. In contrast, apolar crystals were grown from complexes containing p-RBA ligands with R = F and CH3. In all crystals, a polar two-dimensional (2D) layer constructed from the parallel polar [Cu(ii)(p-RBA)2(py)2(H2O)]∞ chain arrangement was formed based on weak van der Waals C-H⋯-O- interactions between the hydrogen atom of py and the carboxylate oxygen atom of the p-RBA ligand. Weak interlayer halogen (X)⋯π and multipoint C-H⋯π interactions played important roles in forming parallel arrangements of polar 2D layers and polar crystals, but there were no effective intermolecular interactions between the polar 2D layers in apolar [Cu(ii)(p-FBA)2(py)2(H2O)] and [Cu(ii)(p-CH3BA)2(py)2(H2O)] crystals. The magnitudes of the interlayer interactions in the polar crystals were larger than those in the apolar ones because of the effective intermolecular interactions. The SHG intensities of the four polar crystals were approximately 0.7 times larger than that of sucrose.

    DOI: 10.1039/c5dt04865f

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  • Stepwise fabrication of donor/acceptor thin films with a charge-transfer molecular wire motif 査読

    Yoshihiro Sekine, Taiga Yokoyama, Norihisa Hoshino, Manabu Ishizaki, Katsuhiko Kanaizuka, Tomoyuki Akutagawa, Masa Aki Haga, Hitoshi Miyasaka

    Chemical Communications   52 ( 97 )   13983 - 13986   2016年

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    掲載種別:研究論文(学術雑誌)  

    Novel thin films composed of a donor (D)/acceptor (A) charge-transfer chain compound were fabricated by a layer-by-layer technique using complexation of a paddlewheel-type diruthenium(ii, ii) complex with an N,N′-dicyanoquinonediimine derivative on an ITO substrate with a pyridine-substituted phosphonate anchor. The stepwise growth of an electron-transfer D+A--chain thin film was confirmed.

    DOI: 10.1039/c6cc08310b

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  • Liquid Crystalline Phase Induced by Molecular Rotator and Dipole Fluctuation 査読

    Qian Chong Zhang, Takashi Takeda, Norihisa Hoshino, Shin Ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa

    Crystal Growth and Design   15 ( 12 )   5705 - 5711   2015年11月

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    掲載種別:研究論文(学術雑誌)  

    The thermal properties, crystal structures, dielectric relaxations, and rotational potential energy curves were examined for new rod-like molecules 1 and 2 bearing three aromatic rings connected by two -CONH- linkage groups to clarify the dynamic molecular behavior and phase transition behavior of the molecular assemblies. The molecular structures of 1 and 2 differed in that the central aromatic ring was phenyl (-C6H4-) in 1 and pyridyl (-C5NH3-) in 2, which affected the phase transition behavior owing to the permanent dipole moment without the center of inversion in molecule 2. Although the crystal structures of 1 and 2 were isostructural, the melting point of crystal 2 was approximately 43 K lower than that of crystal 1, and a smectic A mesophase was reversibly observed in crystal 2. A broad endothermic thermal anomaly of crystal 2 was observed in the heating process on the differential scanning calorimetry chart because of thermally activated dipole fluctuation, which was consistent with the frequency- and temperature-dependent dielectric relaxations. Double- and single-minimum-type potential energy curves were observed in the rotations of -C6H4- and -C5NH3- rings, respectively, from density functional theory calculations. The difference in rotational symmetry affected the crystal lattice energy and appearance of the mesophase.

    DOI: 10.1021/acs.cgd.5b00695

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  • Collective In-Plane Molecular Rotator Based on Dibromoiodomesitylene π-Stacks 査読

    Jun Ichi Ichikawa, Norihisa Hoshino, Takashi Takeda, Tomoyuki Akutagawa

    Journal of the American Chemical Society   137 ( 40 )   13155 - 13160   2015年10月

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    掲載種別:研究論文(学術雑誌)  

    Interest in artificial solid-state molecular rotator systems is growing as they enable systems to be designed for achieving specific physical functions. The phase transition behavior of four halomesitylene crystals indicated dynamic in-plane molecular rotator characteristics in dibromoiodomesitylene, tribromomesitylene, and dibromomesitylene crystals. Such molecular rotation in diiodomesitylene crystals was suppressed by effective I···I intermolecular interactions. The in-plane molecular rotation accompanied by a change in dipole moment resulted in dielectric phase transitions in polar dibromoiodomesitylene and dibromomesitylene crystals. No dielectric anomaly was observed for the in-plane molecular rotation of tribromomesitylene in the absence of this dipole moment change. Typical antiferroelectric-paraelectric phase transitions were observed in the dibromomesitylene crystal, whereas the dielectric anomaly of dibromoiodomesitylene crystals was associated with the collective in-plane molecular rotation of polar π-molecules in the π-stack. We found that the single-rope-like collective in-plane molecular rotator was dominated by intermolecular I···I interactions along the π-stacking column of polar dibromoiodomesitylene.

    DOI: 10.1021/jacs.5b08215

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  • Structural Flexibilities and Gas Adsorption Properties of One-Dimensional Copper(II) Polymers with Paddle-Wheel Units by Modification of Benzoate Ligands 査読

    Kiyonori Takahashi, Norihisa Hoshino, Takashi Takeda, Shin Ichiro Noro, Takayoshi Nakamura, Sadamu Takeda, Tomoyuki Akutagawa

    Inorganic Chemistry   54 ( 19 )   9423 - 9431   2015年9月

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    掲載種別:研究論文(学術雑誌)  

    CO<sub>2</sub> and N<sub>2</sub> gas adsorption/desorption properties of one-dimensional copper(II) polymers with paddle-wheel units [Cu<sup>II</sup><sub>2</sub>(p-XBA)<sub>4</sub>(pyrazine)]<sub>∞</sub> were successfully controlled through the tuning of interchain interactions by modification of para-substituent X groups on the benzoate (BA) ligands (X = Cl, Br, I, and OCH<sub>3</sub>). Although none of the four crystals had sufficient void space to integrate the crystallization solvents, gate-opening gas adsorption and desorption behaviors coupled with structural phase transitions were observed for CO<sub>2</sub> (T = 195 K) and N<sub>2</sub> (T = 77 K), with differences depending on the precise substituent. van der Waals interchain interactions, specifically π···π, halogen···π, and C-H···π contacts, were dominant in forming the crystal lattice; their magnitude was associated with gate-opening pressure and hysteresis behaviors. Both the type and magnitude of the interactions were evaluated by Hirshfeld surface analysis, which indicated that structural flexibility decreased as larger halogen atoms were included. Overall, weak interchain interaction and structural flexibility generated new void spaces to adsorb CO<sub>2</sub> and N<sub>2</sub> gases.

    DOI: 10.1021/acs.inorgchem.5b01168

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  • Protonic Conductivity and Hydrogen Bonds in (Haloanilinium)(H<sub>2</sub>PO<sub>4</sub>) Crystals 査読

    Yuya Yoshii, Norihisa Hoshino, Takashi Takeda, Tomoyuki Akutagawa

    Journal of Physical Chemistry C   119 ( 36 )   20845 - 20854   2015年9月

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    掲載種別:研究論文(学術雑誌)  

    Brønsted acid-base reactions between phosphoric acid (H3PO4) and haloanilines in alcohols formed 1:1 proton-transferred ionic salts of (X-anilinium+)(H2PO4-) and 2:1 ones of (X-anilinium+)2(HPO42-) (X = F, Cl, Br, and I at o, m, and p positions of anilinium). Only the former 1:1 single crystals showed proton conductivity under the N2 condition, and the latter 2:1 crystals became protonic insulators. In crystals, diverse hydrogen-bonding structures from 1D to 2D networks were achieved by modification of the molecular structure of X-anilinium cations. The protonic conductivity was associated with the connectivity of H2PO4- anions in the hydrogen-bonding networks. The hydrogen-bonding ladder chains in (o-cloroanilinim)(H2PO4-) and (o-bromoanilinim)(H2PO4-) resulted in the highest protonic conductivity of 10-3 S cm-1. The protonic conductivity of the ladder-chain (H2PO4-) arrangements was higher than that of 2D sheets. The motional freedom of protons was analyzed by difference Fourier analysis of the single-crystal X-ray structure. The 2D layer, including (H2PO4-)2 dimers and (H2PO4-)4 tetramers, showed relatively low protonic conductivity, and the activation energy for proton conductivity was lowered by increasing the hydrogen-bonding connectivity and uniformity between H2PO4- anions.

    DOI: 10.1021/acs.jpcc.5b06665

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  • Crystal-to-crystal structural transformation of hydrogen-bonding molecular crystals of (imidazolium)(3-hydroxy-2-quinoxalinecarboxylate) through H<sub>2</sub>O adsorption-desorption 査読

    Y. Yoshii, K. Sakai, N. Hoshino, T. Takeda, S. Noro, T. Nakamura, T. Akutagawa

    CrystEngComm   17 ( 31 )   5962 - 5969   2015年8月

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    掲載種別:研究論文(学術雑誌)  

    The Brønsted acid-base reaction between 3-hydroxy-2-quinoxalinecarboxylic acid (Hhqxc) and imidazole (Im) in acetone-H2O yielded two 1:1 salts: anhydrous (HIm+)(hqxc-) (1) and hydrated (HIm+)(hqxc-)·(H2O) (2), where HIm+ and hqxc- are imidazolium and 3-hydroxy-2-quinoxalinecarboxylate, respectively. Single-crystal X-ray structural analyses and vibrational spectra were consistent with the lactam tautomer of the hqxc- anion, which formed π-dimers in both 1 and 2. Each π-dimer in crystal 1 was connected by intermolecular N-H⋯O hydrogen-bonding interactions to form a linear hqxc- chain, whereas the π-dimers in crystal 2 formed an intermolecular N-H⋯O hydrogen-bonding zigzag chain. The HIm+ cations existed in the crystalline space between the hydrogen-bonding hqxc- anionic chains. A reversible crystal-to-crystal structural transformation between crystals 1 and 2 was observed following H2O adsorption-desorption, which was confirmed by powder X-ray diffraction measurements, single-crystal X-ray structural analyses, and H2O adsorption-desorption isotherms at 323 K. The structural rearrangement of the hqxc- anions was achieved through changes in the intermolecular hydrogen-bonding interactions. The temperature- and frequency-dependent dielectric constants of crystal 2 revealed a dielectric peak at ~330 K owing to thermal fluctuations of H2O molecules within the crystal.

    DOI: 10.1039/c4ce02519a

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  • Cation-Anion Dual Sensing of a Fluorescent Quinoxalinone Derivative Using Lactam-Lactim Tautomerism 査読

    Yuta Nakane, Takashi Takeda, Norihisa Hoshino, Ken Ichi Sakai, Tomoyuki Akutagawa

    Journal of Physical Chemistry A   119 ( 24 )   6223 - 6231   2015年6月

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    掲載種別:研究論文(学術雑誌)  

    A quinoxalinone derivative capable of lactam-lactim tautomerization was designed as a new fluorescence probe for sensing of cation (M<sup>+</sup> = Li<sup>+</sup> and Na<sup>+</sup>) and anion (X<sup>-</sup> = F<sup>-</sup>, Cl<sup>-</sup>, Br<sup>-</sup>, and CH<sub>3</sub>COO<sup>-</sup>) in organic solvents. In THF, the minor lactam tautomer exhibited a weak fluorescence band at 425 nm with a typical Stokes shift of ∼4400 cm<sup>-1</sup>, whereas the major lactim tautomer exhibited an intense fluorescence band at 520 nm with large Stokes shift of ∼8900 cm<sup>-1</sup> due to excited-state intramolecular proton transfer (ESIPT). The presence of either cations or anions was found to promote lactim-to-lactam conversion, resulting in the lowering of the ESIPT fluorescence. The lone pairs on the alkylamide oxygen and the quinoxalinone ring nitrogen of the lactam were found to bind Li<sup>+</sup> to form a 1:2 coordination complex, which was confirmed by single crystal X-ray structural analysis and fluorescent titrations. In addition, the N-H bond of the lactam was able to recognize anions via N-H···X hydrogen bonding interactions. Where X = F<sup>-</sup> or CH<sub>3</sub>COO<sup>-</sup>, further addition of these anions caused deprotonation of the lactam to generate an anionic state, consistent with the crystal structure of the anion prepared by mixing tetrabutylammonium fluoride and the quinoxalinone derivative in THF. Dual cation-anion-sensing responses were found to depend on the ion-recognition procedure. The anionic quinoxalinone derivative and its Li<sup>+</sup> complex, which are formed by the addition of CH<sub>3</sub>COO<sup>-</sup> and Li<sup>+</sup>, respectively, displayed different fluorescence enhancement behavior due to the two anions exchanging with each other.

    DOI: 10.1021/acs.jpca.5b02850

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  • Fluorescent Ferroelectrics of Hydrogen-Bonded Pyrene Derivatives 査読

    Hayato Anetai, Yoshifumi Wada, Takashi Takeda, Norihisa Hoshino, Shunsuke Yamamoto, Masaya Mitsuishi, Taishi Takenobu, Tomoyuki Akutagawa

    Journal of Physical Chemistry Letters   6 ( 10 )   1813 - 1818   2015年5月

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    掲載種別:研究論文(学術雑誌)  

    Organic materials with diverse molecular designs show multifunctional properties such as coupled ferroelectric, optical, ferromagnetic, and transport properties. We report the design of an alkylamide-substituted pyrene derivative displaying fluorescent ferroelectric properties coupled with electron transport properties. In solution phase, this compound displayed concentration-dependent fluorescence, whereas in xerogels, a fluorescent green organogel (>0.1 mM) and entangled nanofibers were observed. A discotic hexagonal columnar liquid crystalline phase was observed above 295 K due to intermolecular hydrogen bonding and π-stacking interactions. The direction of the hydrogen-bonded chains could be inverted by the application of an external electric field along the π-stacked column, resulting in ferroelectric polarization-electric field (P-E) hysteresis. The local electric field arising from the ferroelectric macrodipole moment arrangement along the π-stacking direction affected the electron transport properties on the π-stack of pyrenes, thus confirming the current-switching phenomena according to P-E hysteresis. We report that multifunctional properties such as ferroelectricity, fluorescence, and electron transport switching were successfully achieved in hydrogen-bonded dynamic π-molecular assemblies. (Graph Presented).

    DOI: 10.1021/acs.jpclett.5b00703

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  • Three-dimensional architectures of [Mn<sup>ii</sup>Cr<sup>iii</sup>(oxalate)<sub>3</sub>]<sup>-</sup> complexes with cage-type networks surrounding supramolecular cations 査読

    Toru Endo, Kazuya Kubo, Masashi Yoshitake, Shin Ichiro Noro, Norihisa Hoshino, Tomoyuki Akutagawa, Takayoshi Nakamura

    Crystal Growth and Design   15 ( 3 )   1186 - 1193   2015年3月

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    掲載種別:研究論文(学術雑誌)  

    Metal-organic network structure based on oxalate bridges {[MnIICrIII(oxalate)3]-}- and supramolecular cations (H2PPD2+)(benzo[18]crown-6)2[MnCr(oxalate)3](CH3OH)(CH3CN)2 (1) and (o-FAni+)2(DCH[18]crown-6)2[Mn(CH3OH)Cr(oxalate)3][MnCr(oxalate)3](CH3OH) (2), where H2PPD2+, o-FAni+, and DCH[18]crown-6 denote p-phenylenediammonium2+, o-fluoroanilinium+, and cis-syn-cis-dicyclohexano[18]crown-6, respectively, were synthesized. The crystal structure of 1 was the combination of [Mn(A)Cr(A)(oxalate)3]- and [Mn(A)Cr(Δ)(oxalate)3]-, whereas that of crystal 2 was the combination of [Mn(A)(CH3OH)Cr(Δ)(oxalate)3] and [Mn(A)Cr(Δ)(oxalate)3]. Large flexible supramolecular cations provide the three-dimensional structure of {[MnIICrIII(oxalate)3]-}-, which is different from the two-dimensional honeycomb structure often observed for {[MnIICrIII(oxalate)3]-}- complexes. Temperature-dependent magnetic susceptibilities of the complexes 1 and 2 exhibited ferromagnetic behaviors following the Curie-Weiss law (C = 11.5 cm3 K mol-1, θ = 13.0 K for 1; C = 4.14 cm3 K mol-1, θ = 12.3 K for 2).

    DOI: 10.1021/cg501560z

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  • Crystal structure of bis(tetraphenyl-phosphonium) bis(cyanido-κC)-(29H, 31H-tetrabenzo[b,g,l,q]porphinato-κ<sup>4</sup>N<sup>29</sup>,N<sup>30</sup>,N<sup>31</sup>,N<sup>32</sup>)ferrate(II) acetone disolvate 査読

    Miki Nishi, Masaki Matsuda, Norihisa Hoshino, Tomoyuki Akutagawa, M. Weil

    Acta Crystallographica Section E: Structure Reports Online   71 ( 2 )   m48 - m49   2015年2月

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    掲載種別:研究論文(学術雑誌)  

    The crystal structure of the title compound, (C24H20P)2[Fe(C36H20N4)(CN)2]·2C3H6O, is constructed from a tetrahedral Ph4P+ (tetraphenylphosphonium) cation, one [Fe(tbp)(CN)2]2- anion (tbp = tetrabenzoporphyrin in its doubly deprotonated form), located on a centre of inversion, and an acetone molecule as crystallization solvent. Since the molecular structure of the M(tbp) moiety is insensitive to the kind of metal ion and its oxidation state, bond lengths and angles in the [Fe(tbp)(CN)2]2- anion are similar to those in other M(tbp) compounds. The Fe2+ ion, located on a centre of inversion, is coordinated by four N atoms of tpb in the equatorial plane and by two C atoms of the cyanide anion at axial positions in a slightly distorted octahedral configuration. The packing is stabilized by C - H⋯N interactions between the Ph4P cation and the CN ligand of the [Fe(tbp)(CN)2]2-anion, and by C - H⋯π interactions between the Ph4P+ cation, acetone solvent molecules and the [Fe(tbp)(CN)2]2-anion.

    DOI: 10.1107/S2056989015001735

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  • Crystal structures and redox responses coupled with ion recognition of p-benzoquinone- And hydroquinone-fused [18]crown-6 査読

    Takayuki Kobayashi, Yuta Nakane, Takashi Takeda, Norihisa Hoshino, Hidetoshi Kawai, Tomoyuki Akutagawa

    Chemistry - An Asian Journal   10 ( 2 )   390 - 396   2015年2月

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    掲載種別:研究論文(学術雑誌)  

    The crystal structures and redox properties of p-benzoquinone (BQ)-fused [18]crown-6 1 and bis-BQ-fused [18]crown-6 2 were examined. The anion radicals of these BQ molecules were stabilized by addition of metal ions, through effective electrostatic interactions between the negatively charged BQ moiety and positively charged ion-capturing [18]crown-6 unit. The electrostatic interactions and solvation energy played important roles in determining the magnitudes of anodic redox shifts in the reduction potentials. Regular π-stacking of BQ units and regular arrays of [18]crown-6 units were observed in crystal 2, in which onedimensional π-electron columns were separated by ionic channels. The hydroquinone-fused [18]crown-6 molecule 3 and a new BQ- and phenol-fused [18]crown-6 derivative 4 were obtained as single crystals. The molecular conformations of [18]crown-6 in crystal 3 and hydrated crystal 3·H2O were different from each other.

    DOI: 10.1002/asia.201403262

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  • Mesophases and ionic conductivities of simple organic salts of M(m-iodobenzoate) (M = Li<sup>+</sup>, Na<sup>+</sup>, K<sup>+</sup>, Rb<sup>+</sup>, and Cs<sup>+</sup>) 査読

    Manami Endo, Yuta Nakane, Kiyonori Takahashi, Norihisa Hoshino, Takashi Takeda, Shin Ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa

    Journal of Physical Chemistry B   119 ( 4 )   1768 - 1777   2015年1月

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    掲載種別:研究論文(学術雑誌)  

    Simple organic salts such as (Li+)(m-IBA) (1), (Na+)(m-IBA) (2), (K+)(m-IBA) (3), (Rb+)(m-IBA) (4), and (Cs+)(m-IBA) (5) (m-IBA = m-iodobenzoate) were shown to form a mesophase before crystal melting or decomposition. The crystals were obtained in the hydrated form, e.g., 1·(H2O), 2· (H2O), 3·0.5(H2O), 4·(H2O), and 5·(H2O); they were then converted into dehydrated forms by increasing the temperature to ∼450 K. Optically anisotropic-layered mesophases were observed in unhydrated crystals 2, 3, 4, and 5, whereas an optically isotropic mesophase (e.g., rotator phase) was found for crystal 1. The single-crystal X-ray structural analysis of the hydrated crystals revealed an inorganic-organic alternate layer structure, which is consistent with the average molecular orientation in the layered mesophase. The m-IBA anions formed a π-stacking columnar structure in the hydrated crystals, while one- or two-dimensional M+∼O networks were observed in the inorganic layers. Our results showed that the M+∼ O interactions and their connectivity are strongly influenced by the size of the cations. The reconstruction of the M+∼O networks by removing H2O molecules was crucial for the formation of the mesophases. A strong response of both the real and imaginary parts of the dielectric constant was observed around the solid-mesophase phase-transition temperatures of crystals 1-5, with the ionic conductions playing a critical role.(Figure Presented).

    DOI: 10.1021/jp5112026

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  • Comparison of structural and electrical characteristics between tetrabenzoporphyrinand phthalocyanine-based charge-transfer complexes 査読

    Miki Nishi, Masaki Matsuda, Norihisa Hoshino, Tomoyuki Akutagawa

    Chemistry Letters   44 ( 3 )   390 - 392   2015年

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    掲載種別:研究論文(学術雑誌)  

    A charge-transfer complex based on axially CN-substituted iron tetrabenzoporphyrin has been fabricated. X-ray structure analysis reveals that the differences in the distances and angles around the meso positions between tetrabenzoporphyrin and phthalocyanine are substantial between the porphin and porphyrazine frameworks. Electrical transport measurements reveal semiconducting behavior with higher activation energy due to the reduction in ππ overlapping, compared to an isostructural phthalocyanine complex.

    DOI: 10.1246/cl.141123

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  • A cubic dipole lattice of water molecules trapped inside carbon cages 査読

    Shinobu Aoyagi, Norihisa Hoshino, Tomoyuki Akutagawa, Yuki Sado, Ryo Kitaura, Hisanori Shinohara, Kunihisa Sugimoto, Rui Zhang, Yasujiro Murata

    Chemical Communications   50 ( 5 )   524 - 526   2014年12月

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    掲載種別:研究論文(学術雑誌)  

    We report the crystal structure and dielectric properties of a pure H2O@C60 crystal at low temperature. The caged water molecules free from the hydrogen bonds rotate even at 8 K. The antifreeze rotating water molecules respond to an external electric field due to their permanent dipole moment. © 2013 The Royal Society of Chemistry.

    DOI: 10.1039/c3cc46683c

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  • Synthetic-method-dependent magnetic relaxation in a cobalt(II) phosphonate chain compound 査読

    Zhong Sheng Cai, Min Ren, Song Song Bao, Norihisa Hoshino, Tomoyuki Akutagawa, Li Min Zheng

    Inorganic Chemistry   53 ( 23 )   12546 - 12552   2014年12月

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    掲載種別:研究論文(学術雑誌)  

    A polar cobalt(II) phosphonate Co(bamdpH2)(H2O) (1) [bamdpH4 = (benzylazanediyl)bis(methylene)diphosphonic acid] is reported. It shows a linear chain structure. The neighboring chains are connected by moderately strong hydrogen bonds forming a supramolecular layer. The interlayer spaces are filled with the organic groups of the phosphonate ligands. Compound 1 displays the coexistence of single-chain magnet behavior and canted antiferromagnetism below 2.8 K. Moreover, the magnetic dynamics is strongly dependent on the synthetic methods, a phenomenon that has not been documented before.

    DOI: 10.1021/ic5021737

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  • Molecular assembly and ferroelectric response of benzenecarboxamides bearing multiple -CONHC<sub>14</sub>H<sub>29</sub> chains 査読

    Yuta Shishido, Hayato Anetai, Takashi Takeda, Norihisa Hoshino, Shin Ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa

    Journal of Physical Chemistry C   118 ( 36 )   21204 - 21214   2014年9月

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    掲載種別:研究論文(学術雑誌)  

    Five simple benzenecarboxamide (BC) derivatives bearing multiple -CONHC14H29 chains-N,N′-bis(tetradecyl)-1,4-benzenedicarboxamide (2BC), N,N′,N-tri(tetradecyl)-1,3,5-benzenetricarboxamide (3BC), N,N′,N,N-tetra(tetradecyl)-1,2,4,5-benzenetetracarboxamide (4BC), N,N′,N,N′,N′′′′-penta(tetradecyl)benzenepentacarboxamide (5BC), and N,N′,N,N′,N′′′′,N′′′′′-hexa(tetradecyl)benzenehexacarboxamide (6BC)-were examined in terms of their molecular assemblies in solution, organogels, liquid crystals, and solids as well as their phase transition behavior and dielectric responses. The molecular assemblies of compounds 3BC-6BC were dominated by the intermolecular N-H∼O= hydrogen-bonding interactions along the π-stacking directions and formed one-dimensional π-stacking nanofibers. The excellent organogelation characteristics of compound 3BC were observed in common organic solvents such as ethanol, acetonitrile, acetone, and N,N-dimethylformamide, whereas compounds 4BC and 6BC formed organogels in hexane and/or toluene. Mechanical fraying of the three-dimensional entangled nanofibers in the organogel state resulted in a two-dimensional cobweb-like nanofiber network, where the typical height and width of each nanofiber on the substrate surface were ca. 3.5 and 200 nm, respectively. A single nanofiber was constructed by a π-stacking column through intermolecular N-H∼O= hydrogen-bonding interactions, of which the hexagonal arrangement resulted in ordered hexagonal columnar (Colho) discotic liquid crystalline phases for compounds 3BC-6BC. Both of the intercolumnar and intracolumnar distances in the Colho phase were linearly increased according to the number of -CONHC14H29 chains. The temperature- and frequency-dependent dielectric constants of compounds 2BC-6BC in cast-films revealed dielectric anomalies around the solid to Colho phase transition temperatures due to thermally activated molecular motion. Polarization-electric field (P-E) curves of compounds 2BC, 3BC, and 5BC in the mesophases showed hysteretic behavior with ferroelectric ground states, whereas paraelectric behavior with linear P-E dependence was observed for compounds 4BC and 6BC.

    DOI: 10.1021/jp506035h

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  • Novel method for the fabrication of a charge-transfer complex crystal by photoirradiation 査読

    Masaki Matsuda, Miki Nishi, Shoko Koga, Mika Fujishima, Norihisa Hoshino, Tomoyuki Akutagawa, Hiroyuki Hasegawa

    Chemistry - A European Journal   20 ( 36 )   11318 - 11321   2014年9月

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    掲載種別:研究論文(学術雑誌)  

    A novel method for the fabrication of a charge-transfer complex crystal was developed. Photoirradiation of a solution of TPP[Co(tbp)(CN)2] and TPP[Co(Pc)(CN)2] (tbp=tetrabenzoporphyrin, Pc=phthalocyanine, TPP=tetraphenylphosphonium) gave a molecular conducting crystal of a charge-transfer complex TPP[Co(tbp)(CN)2]2, which was produced by the process in which the photoexcited electron in tbp was transferred from the LUMO of tbp to that of Pc. Crystal growth: Photoirradiation of a solution of TPP[Co(tbp)(CN)2] and TPP[Co(Pc)(CN)2] (tbp=tetrabenzoporphyrin, Pc=phthalocyanine, TPP=tetraphenylphosphonium) gave a molecular conducting crystal of a charge-transfer complex TPP[Co(tbp)(CN) 2]2, which was produced by the process in which the photoexcited electron in tbp was transferred from the LUMO of tbp to that of Pc (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/chem.201402644

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  • Thermally driven polymorphic transition prompting a naked-eye-detectable bending and straightening motion of single crystals 査読

    Tatsuya Shima, Takahiro Muraoka, Norihisa Hoshino, Tomoyuki Akutagawa, Yuka Kobayashi, Kazushi Kinbara

    Angewandte Chemie - International Edition   53 ( 28 )   7173 - 7178   2014年7月

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    掲載種別:研究論文(学術雑誌)  

    The amplification of molecular motions so that they can be detected by the naked eye (107-fold amplification from the ångström to the millimeter scale) is a challenging issue in the development of mechanical molecular devices. In this context, the perfectly ordered molecular alignment of the crystalline phase has advantages, as demonstrated by the macroscale mechanical motions of single crystals upon the photochemical transformation of molecules. In the course of our studies on thermoresponsive amphiphiles containing tetra(ethylene glycol) (TEG) moieties, we serendipitously found that thermal conformational changes of TEG units trigger a single-crystal-to-single- crystal polymorphic phase transition. The single crystal of the amphiphile undergoes bending and straightening motion during both heating and cooling processes at the phase-transition temperatures. Thus, the thermally triggered conformational change of PEG units may have the advantage of inducing mechanical motion in bulk materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/anie.201402560

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  • Crystal structures, dielectric, and CO<sub>2</sub>-adsorption properties of one-dimensional [Cu(II)<sub>2</sub>(adamantane-1-carboxylate)<sub>4</sub>(pyrazine)]∞ coordination polymers with polar ligands 査読

    Kiyonori Takahashi, Norihisa Hoshino, Shin Ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa

    Science of Advanced Materials   6 ( 7 )   1417 - 1424   2014年7月

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    掲載種別:研究論文(学術雑誌)  

    Cu(II) binuclear coordination polymers of [Cu(II)(ADCOO)4(pz)]∞ (1), [Cu(II)(ADCOO)4(F-pz)]∞ (2), and [Cu(II)(Cl-ADCOO)4(pz)]∞ (3) were prepared, where ADCOO, Cl-ADCOO, pz, and F-pz are adamantane-1- carboxylate, 3-chloroadamantane-1-carboxylate, pyrazine, and 2-fluoropyrazine, respectively. The Cu(II) binuclear units of [Cu(II)(ADCOO)4] and [Cu(II)(Cl-ADCOO)4] were formed by the four bridging ligands of ADCOO and Cl-ADCOO to the two Cu(II) ions, respectively, which were further connected by the axial bidentate ligands of pz or F-pz, to form one-dimensional (1D) coordination polymers. Although the 1D coordination polymers were observed in the typical structures of crystals 1, 2, and 3, the packing structure of polymer 3 was different from those of crystals 1 and 2. Three-dimensional (3D) interdigitated polymer arrays were observed in 1 and 2 as cubic crystal systems with the I-43d space group, whereas the two-dimensional array of 1D polymers of 3 was the same as that of the [Cu(II)(C6H5COO)4(pz)]∞ crystal. The crystal structure of 2 was not affected by the introduction of a polar F group into the axial pz ligand, whereas the introduction of the Cl-substituent into the ADCOO ligand significantly modified the packing structure of the coordination polymers. The polar ligands of F-pz in 2 and Cl-ADCOO in 3 were static at 110 K according to X-ray crystal structural analyses. The absolute magnitude of the dielectric constants was decreased in the order of 3, 2, and 1, which is consistent with the dipole moments of the ligands. No CO2 gas adsorption-desorption processes were observed in crystals 1, 2, and 3 at 195 K. The 3D interdigitated polymer arrangements in 1 and 2, and the strong dipole- dipole interaction between Cl-ADCOO ligands, were not responsible for the structural changes in the CO2 gas adsorption-desorption. © 2014 by American Scientific Publishers.

    DOI: 10.1166/sam.2014.1831

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  • Crystal structures, CO<sub>2</sub> adsorption, and dielectric properties of [Cu(II)<sub>2</sub>(R-benzoate)<sub>4</sub>(pyrazine)]<sub>∞</sub> polymers (R = m-F, 2,3-F<sub>2</sub>, m-Cl, and m-CH<sub>3</sub>) 査読

    Kiyonori Takahashi, Norihisa Hoshino, Takashi Takeda, Shin Ichiro Noro, Takayoshi Nakamura, Sadamu Takeda, Tomoyuki Akutagawa

    Dalton Transactions   43 ( 24 )   9081 - 9089   2014年6月

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    掲載種別:研究論文(学術雑誌)  

    m-Fluorobenzoate (m-FBA), 2,3-difluorobenzoate (2,3-F2BA), m-methylbenzoate (m-MBA), and m-chlorobenzoate (m-ClBA) were introduced into the Cu(II) binuclear unit as bridging ligands between two Cu(II) sites, which were further connected by an axial pyrazine (pz) ligand to form one-dimensional coordination polymers of [Cu(II)2(m-FBA)4(pz)] ∞ (1), [Cu(II)2(2,3-F2BA) 4(pz)]∞ (2), [Cu(II)2(m-MBA) 4(pz)]∞ (3), and [Cu(II)2(m-ClBA) 4(pz)]∞ (4), respectively. The parallel arrangements of one-dimensional (1D) polymers result in 1D channels between the polymers that crystallization CH3CN molecules can occupy to form single crystals of 1·4CH3CN, 2·4CH3CN, 3·2CH3CN, and 4·2CH3CN. Both π-dimer and dipole-dipole interactions were simultaneously observed in the interchain interactions of m-FBA and/or 2,3-F2BA ligands in crystals 1 and 2. The sizes of the one-dimensional channels between the polymers are thus modulated according to the interchain interactions between the polar BA ligands. CH3CN molecules within the channels were easily replaced by H 2O under ambient conditions. CO2 adsorption-desorption isotherms of crystals 1, 2, and 3 at 195 K indicated gate-adsorption with a hysteresis, whereas two-step gate-adsorption behavior was observed for CO 2 in crystal 4. Temperature- and frequency-dependent dielectric responses were not observed in crystals 1-4 under vacuum conditions, whereas dielectric anomalies were observed around 290 K for crystals 1 and 2 with adsorbed CO2. CO2 desorption from the channels in crystals 1 and 2 activated the molecular motions of polar BA ligands and dielectric responses around 290 K, which were confirmed from CO2 adsorption-desorption isotherms around 290 K and differential scanning calorimetries under CO2 conditions. © the Partner Organisations 2014.

    DOI: 10.1039/c4dt00258j

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  • Polar metal phosphonate containing unusual μ<sub>4</sub>-OH bridged double chains showing canted antiferromagnetism with large coercivity 査読

    Xiao Jing Yang, Song Song Bao, Min Ren, Norihisa Hoshino, Tomoyuki Akutagawa, Li Min Zheng

    Chemical Communications   50 ( 30 )   3979 - 3981   2014年3月

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    掲載種別:研究論文(学術雑誌)  

    The first examples of metal phosphonates based on an asymmetrical 2-(phosphonomethyl)benzoic acid (2-pmbH3) are reported, namely, Co2(μ4-OH)(2-pmb) (1) and Cu4(μ3-OH)2(2-pmb)2 (2). Both crystallize in polar space groups and show layered structures. Compound 1 contains unusual μ4-OH bridged double chains of (Co2(μ4-OH)O3), inter-connected by the phosphonate groups. In 2, chair-like tetramers of Cu4(μ3-OH)O2 are linked by both carboxylate and phosphonate groups. Magnetic studies reveal that compound 1 experiences canted antiferromagnetic ordering below 31.0 K with a large coercivity of 4.3 Tesla at 2 K. © 2014 The Partner Organisations.

    DOI: 10.1039/c3cc45976d

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  • The formation of organogels and helical nanofibers from simple organic salts 査読

    Yuya Yoshii, Norihisa Hoshino, Takashi Takeda, Hiroki Moritomo, Jun Kawamata, Takayoshi Nakamura, Tomoyuki Akutagawa

    Chemistry - A European Journal   20 ( 49 )   16279 - 16285   2014年1月

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    掲載種別:研究論文(学術雑誌)  

    Simple organic salts based on aniline-derived cations and D-tartrate anions formed organogels and helical nanofibers. The organic salt (p-fluoroanilinium)(D-tartrate) was found to generate an organogel despite the absence of a hydrophobic alkyl chain, whereas (p-iodoanilinium)(D-tar-trate) formed helical nanofibers in braided ropelike structures through a rolling-up process. The helicity of these nanofibers could be reversed by changing the growth solvent. The driving forces responsible for the formation of the nanofibers were determined to be 1D O-H···O∼ hydrogen-bonding interactions between D-tartrate anions and p stacking of anilinium cations, as well as steric hindrance between the hydrogen-bonded chains.

    DOI: 10.1002/chem.201404043

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  • Multi-functional molecular rotators with dielectric, magnetic and optical responses 査読

    Norihisa Hoshino, Takashi Takeda, Tomoyuki Akutagawa

    RSC Advances   4 ( 2 )   743 - 747   2014年

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    掲載種別:研究論文(学術雑誌)  

    The phase transition mechanism of AZADO radical has been examined in terms of the molecular rotation. Drastic changes in optical, magnetic and dielectric properties associated with the phase transition can be explained by molecular rotation and an associated order-disorder transition. © The Royal Society of Chemistry 2014.

    DOI: 10.1039/c3ra44515a

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  • Carrier concentration dependent conduction in insulator-doped donor/acceptor chain compounds 査読

    Masaki Nishio, Norihisa Hoshino, Wataru Kosaka, Tomoyuki Akutagawa, Hitoshi Miyasaka

    Journal of the American Chemical Society   135 ( 47 )   17715 - 17718   2013年11月

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    掲載種別:研究論文(学術雑誌)  

    On the basis of the concept that the design of a mixed valence system is a key route to create electronic conducting frameworks, we propose a unique idea to rationally produce mixed valency in an ionic donor/acceptor chain (i.e., D+A- chain). The doping of a redox-inert (insulator) dopant (P) into a D+A- chain in place of neutral D enables the creation of mixed valency A0/A- domains between P units: P-(D+A-)nA0-P, where n is directly dependent on the dopant ratio, and charge transfer through the P units leads to electron transport along the framework. This hypothesis was experimentally demonstrated in an ionic DA chain synthesized from a redox-active paddlewheel [Ru2II,II] complex and TCNQ derivative by doping with a redox-inert [Rh2II,II] complex. © 2013 American Chemical Society.

    DOI: 10.1021/ja409785a

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  • Solvent responsive magnetic dynamics of a dinuclear dysprosium single-molecule magnet 査読

    Min Ren, Song Song Bao, Norihisa Hoshino, Tomoyuki Akutagawa, Bingwu Wang, Yu Chen Ding, Shiqiang Wei, Li Min Zheng

    Chemistry - A European Journal   19 ( 29 )   9619 - 9628   2013年7月

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    掲載種別:研究論文(学術雑誌)  

    A new dysprosium(III) phosphonate dimer {Dy(notpH4)(NO 3)(H2O)}2×8 H2O (1) [notpH6=1,4,7-triazacyclononane-1,4,7-triyl-tris(methylenephosphonic acid)] that contains two equivalent DyIII ions with a three-capped trigonal prism environment is reported. Complex 1 can be transformed into {Dy(notpH4)(NO3)(H2O)}2 (2) in a reversible manner by desorption and absorption of solvent water at ambient temperature. This process is accompanied by a large dielectric response. Magnetic studies reveal that both 1 and 2 show thermally activated magnetization relaxation as expected for single-molecule magnets. Moreover, the magnetic dynamics of the two compounds can be manipulated by controlling the number of solvent molecules at room temperature. Under control! The magnetic dynamics of a dinuclear single-molecule magnet {Dy(notpH4)(NO3)(H 2O)}2× 8 H2O (see figure; notpH 6=1,4,7-triazacyclononane-1,4,7-triyltris(methylenephosphonic acid)) can be manipulated by controlling the number of solvent molecules at room temperature. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/chem.201300497

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  • Structural and spectroscopic study of 6,7-dicyano-substituted lumazine with high electron affinity and proton acidity 査読

    Ken Ichi Sakai, Kenta Nagahara, Yuuya Yoshii, Norihisa Hoshino, Tomoyuki Akutagawa

    Journal of Physical Chemistry A   117 ( 17 )   3614 - 3624   2013年5月

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    掲載種別:研究論文(学術雑誌)  

    The introduction of cyano groups into lumazine (pteridine-2,4-(1H,3H)dione) at the C6 and C7 positions enhances its electron affinity, proton acidity, and solubility in solvents. As a result, 6,7-dicyanolumazine (DCNLH2) forms charge transfer (CT) complexes with donors such as tetrathiafulvalene, 2,3,5,6-tetramethyl-1,4-phenylenediamine, and 3,3′,5,5′- tetramethylbenzidine and readily dissociates a proton from the N1 nitrogen to form a monoanionic salt with tetrabutylammonium (TBA+). Crystal structures of the CT complexes consist of mixed stacks in which DCNLH 2 interacts with donors in face-to-face configurations, but they form intermolecular hydrogen bonds differently depending on the donor type. In the TBA+ salt, two deprotonated DCNLH- monoanions form a unique dianionic dimer connected by two centrosymmetric hydrogen bonds, N3-H···O-C2, which is electronically isolated by the presence of bulky TBA+ countercations and the absence of a proton at the N1 hydrogen-bonding site. This dimer fluoresces yellowish green (fluorescence quantum yield Φ = 0.04). Because the DCNLH- anion only shows weak blue fluorescence in aqueous solution (Φ < 0.01), we suggest that the dimer formation is responsible for the fluorescence enhancement with a large emission band shift to the low-energy side. © 2013 American Chemical Society.

    DOI: 10.1021/jp401528c

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  • Single molecule magnets with m-fluorobenzoate and difluoromethylacetate as polar ligands 査読

    Norihisa Hoshino, Takuya Shiga, Hiroki Oshio, Tomoyuki Akutagawa

    Dalton Transactions   42 ( 13 )   4377 - 4385   2013年4月

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    掲載種別:研究論文(学術雑誌)  

    Two new single molecule magnets (SMMs), [Mn12O 12(CHF2COO)16(H2O) 4]·2CH2Cl2·4H2O (1) and [Mn12O12(m-FPhCOO)16(H2O) 4]·2(m-FPhCOOH)·7CH2Cl2 (2), based on a disc-shaped {Mn12O12}-framework with difluoromethylacetate (CHF2COO-) and m-fluorobenzoate (m-FPhCOO-) as polar ligands were prepared in CH2Cl 2. Structural analyses by X-ray diffraction at 100 K showed orientationally disordered fluorine atoms in the CHF2COO- and m-FPhCOO- ligands of crystals 1 and 2, respectively. In crystal 1, the fluorine atoms at the axial coordination sites of the disc-like {Mn 12O12}-framework exhibited large thermal parameters even at 100 K, suggesting that thermally activated rotation of the -CHF2 groups along the C-COO axis occurred in the CHF2COO- ligands. The SMMs behaviors of crystals 1 and 2 showed magnetization hysteresis at 1.8 K and frequency-dependent in-phase and out-of-phase ac magnetic susceptibilities, characteristic of SMMs. Frequency-dependent dielectric responses as well as two Debye-type relaxation processes at ∼100 and ∼220 K were observed in crystal 1, while such responses were not observed in crystal 2. The activation energy and blocking temperature of the relaxation process for 1 were 12 kJ mol-1 and 48 K, respectively, at ∼100 K, whereas those at ∼220 K were 66 kJ mol-1 and 153 K, respectively. In 1, the two polarization types at ∼100 and ∼220 K were associated with thermally activated fluctuations of the hydrogen-bonded crystalline H2O molecules and rotation of the -CHF2 group in the CHF2COO- ligand. © The Royal Society of Chemistry 2013.

    DOI: 10.1039/c2dt32498a

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  • Molecular motion in pyridazinium/crown ether supramolecular cation salts of a nickel dithiolene complex 査読

    Zun Qi Liu, Kazuya Kubo, Li Lin, Norihisa Hoshino, Shin Ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura

    Dalton Transactions   42 ( 8 )   2930 - 2939   2013年2月

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    掲載種別:研究論文(学術雑誌)  

    Supramolecular cations formed by monoprotonated pyridazinium cations and cis-anti-cis-dicyclohexano[18]-crown-6 (DCH[18]-crown-6) or dibenzo[18]-crown-6 (DB[18]-crown-6) were introduced into [Ni(dmit)2]- salts (where dmit2- = 2-thione-1,3-dithiole-4,5-dithiolate). X-ray crystal structure analysis of (pyridazinium+)(DCH[18]-crown-6)[Ni(dmit) 2]- (1) revealed a chair-type conformation of the DCH[18]-crown-6 moiety. A V-shaped conformation of the DB[18]-crown-6 moiety was observed in (pyridazinium+)(DB[18]-crown-6)2[Ni(dmit) 2]-(H2O)2 (2). Nitrogen atoms in the pyridazinium cations interacted with the oxygen atoms of the DCH[18]-crown-6 and DB[18]-crown-6 through N-H+∼O hydrogen bonds, forming 1:1 and 1:2 supramolecular structures, respectively. Sufficient space for molecular motions of the pyridazinium cations, namely flip-flop and in-plane rotations, exists in salt 1. Disorder in nitrogen atoms was observed by X-ray analysis, indicating dynamic motion of the pyridazinium cation, namely flip-flop motion and in-plane motion. A potential energy calculation further supported the possibility of dynamic motion of cations in the crystal. By contrast, the flip-flop motion of the pyridazinium group in salt 2 is restricted by the two nearest-neighbouring DB[18]-crown-6 molecules. Weak antiferromagnetic intermolecular interactions between the [Ni(dmit)2]- anions in the two-dimensional layers of salt 1 were observed, resulting in alternating antiferromagnetic Heisenberg chain-type magnetic susceptibility. Quasi-one-dimensional intermolecular interactions between the [Ni(dmit) 2]- anions were observed in salt 2, whose magnetic behaviour followed the Bonner-Fisher model. © 2013 The Royal Society of Chemistry.

    DOI: 10.1039/c2dt32542j

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  • Supramolecular rotators of (aniliniums)([18]crown-6) in electrically conducting [Ni(dmit)<sub>2</sub>] crystals 査読

    Norihisa Hoshino, Yuuya Yoshii, Masaki Aonuma, Kazuya Kubo, Takayoshi Nakamura, Tomoyuki Akutagawa

    Inorganic Chemistry   51 ( 23 )   12968 - 12975   2012年12月

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    掲載種別:研究論文(学術雑誌)  

    Supramolecular assemblies of anilinium (Ani+) and fluoroanilinium derivatives (FAni+) with [18]crown-6 were introduced into electrically conducting [Ni(dmit)2] crystals (dmit2- is 2-thioxo-1,3-dithiole-4,5-dithiolate). The crystal structures, electrical conductivities, and magnetic susceptibilities of four new crystals of (Ani +)([18]crown-6)[Ni(dmit)2]3 (1), (o-FAni +)([18]crown-6)[Ni(dmit)2]3 (2), (m-FAni +)([18]crown-6)[Ni(dmit)2]3 (3), and (p-FAni+)([18]crown-6)[Ni(dmit)2]3 (4) were examined from the viewpoint of dynamic supramolecular rotator structures within the crystals. The crystal structures, electrical conduction, and magnetic properties were classified into group-I (crystals 1 and 4) and group-II (crystals 2 and 3). The hydrogen-bonding interaction between -NH 3+ and the oxygen atoms of [18]crown-6 formed the stand-up configuration of rotator-stator structures of (Ani+)([18]crown-6) and (FAni+)([18]crown-6) supramolecules. The potential energy barriers for the 2-fold flip-flop motion of phenyl- and p-fluorophenyl-rings in crystals 1 and 4 had a relatively small magnitude of ∼150 kJmol -1, suggesting that rotations of Ani+ and p-FAni + cations around the C-NH3+ axis occurred in the crystals. In contrast, a large magnitude of the potential energy barriers for the rotations of o-FAni+ and m-FAni+ cations in crystals 2 and 3 (>600 kJmol-1) resulted in static supramolecular cationic structures. The cation:anion ratio of 1:3 in these crystals yielded a trimer φ-stack of [Ni(dmit)2] with a semiconductor-like temperature dependence. The magnetic susceptibilities of the static crystals 2 and 3 were reproduced by the one-dimensional antiferromagnetic linear Heisenberg chain through the one-dimensional linear trimer arrangement. The magnetic susceptibilities of dynamic crystals 1 and 4 enhanced electron delocalization through the intratrimer and intertrimer interactions within the trimer stack, where the molecular rotations of Ani+ and p-FAni+ cations played an important role. © 2012 American Chemical Society.

    DOI: 10.1021/ic302093b

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  • Structural phase transitions induced by molecular motions within an (anilinium)(l-tartrate) ionic molecular crystal 査読

    Yuuya Yoshii, Norihisa Hoshino, Takayoshi Nakamura, Tomoyuki Akutagawa

    CrystEngComm   14 ( 21 )   7458 - 7465   2012年11月

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    掲載種別:研究論文(学術雑誌)  

    Ionic molecular crystals of (anilinium<sup>+</sup>)(l-tartrate<sup>-</sup>) were prepared in C<sub>2</sub>H<sub>5</sub>OH-H<sub>2</sub>O via Bronsted acid-base reaction between aniline and l-tartaric acid. Strong intermolecular O-H⋯O<sup>-</sup> hydrogen-bonding interactions between the terminal -COOH and -COO<sup>-</sup> groups of the l-tartrate<sup>-</sup> monoanion (l-HTart<sup>-</sup>) are essential in forming the one-dimensional hydrogen-bonding (l-HTart<sup>-</sup>)<sub>∞</sub> chains. Furthermore, N-H<sup>+</sup>⋯O<sup>-</sup> hydrogen-bonding interactions between l-HTart<sup>-</sup> and the ammonium moiety of anilinium (Ani<sup>+</sup>) form a π-stacking arrangement of the Ani<sup>+</sup> cations that are orthogonal to the (l-HTart<sup>-</sup>)<sub>∞</sub> chains. DSC analysis revealed a two-step behavior with reversible phase transitions at ∼220 and ∼270 K, in which three types of crystal phases (I, T < 220 K; II, 220 < T < 270 K; III, 270 K < T) were identified. Phase I possesses the same acentric space group (P1), while its unit cell volume is half of that of phases II and III, in which the π-stacking periodicity of the Ani<sup>+</sup> cations of phases II and III are double that of phase I. Although the conformation of the hydroxy (-OH) groups of l-HTart<sup>-</sup> of phase II (T = 250 K) was identical to that of phase I (T = 100 K), the rotation of the C-OH bond (activation energy of ∼70 kJ mol<sup>-1</sup>) was observed for phase III. The thermal fluctuation of the polar -OH group in phase III was dominated by a single minimum-type potential energy curve, as evaluated from the calculations. The temperature- and frequency-dependent dielectric constants suggested a low-frequency thermal fluctuation at temperatures above ∼250 K. © 2012 The Royal Society of Chemistry.

    DOI: 10.1039/c2ce25945a

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  • Three-way switching in a cyanide-bridged [CoFe] chain 査読

    Norihisa Hoshino, Fumichika Iijima, Graham N. Newton, Norifumi Yoshida, Takuya Shiga, Hiroyuki Nojiri, Akiko Nakao, Reiji Kumai, Youichi Murakami, Hiroki Oshio

    Nature Chemistry   4 ( 11 )   921 - 926   2012年11月

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    掲載種別:研究論文(学術雑誌)  

    Bistable compounds that exist in two interchangeable phases under identical conditions can act as switches under external stimuli. Among such switchable materials, coordination complexes have energy levels (or phases) that are determined by the electronic states of their constituent metal ions and ligands. They can exhibit multiple bistabilities and hold promise in the search for multifaceted materials that display different properties in different phases, accessible through the application of contrasting external stimuli. Molecular systems that exhibit both thermo- and photoinduced magnetic bistabilities are excellent candidates for such systems. Here we describe a cyanide-bridged [CoFe] one-dimensional chiral coordination polymer that displays both magnetic and electric bistabilities in the same temperature range. Both the electric and magnetic switching probably arise from the same electron-transfer coupled spin-transition phenomenon, which enables the reversible conversion between an insulating diamagnetic phase and either a semiconducting paramagnetic (thermoinduced) or a type of ferromagnetic single-chain magnet (photoinduced) state. © 2012 Macmillan Publishers Limited. All rights reserved.

    DOI: 10.1038/nchem.1455

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  • Incorporation of cationic electron donor of Ni-pyridyltetrathiafulvalene with anionic electron acceptor of polyoxometalate 査読

    Ryo Tsunashima, Takumi Matsumoto, Norihisa Hoshino, Wataru Niiho, Mizuki Kimura, Kei Kondo, Yoshihiko Suyama, Yukihiro Nishioka, Jun Kawamata, Shin Ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa, Katsuya Ishiguro

    Dalton Transactions   41 ( 33 )   10060 - 10064   2012年9月

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    掲載種別:研究論文(学術雑誌)  

    A new salt - [Ni II(DMSO) 5(TTFPy)] 2[α -SiW 12O 40] (1) - based on polyoxometalates was prepared by coordinating a cationic electron donor of pyridyltetrathiafulvalene (TTFPy) with Ni II. Although the TTFPy molecule did not form a salt with the anionic α-[SiW VI12O 40] 4- because of the weak charge-transfer (CT) interaction, the coordination of Ni with the pyridyl moiety permitted salt formation driven by electrostatic interaction, giving a single crystal of 1. Crystallographic analysis, UV-vis and IR spectroscopy and electrochemical characterization revealed that the fully oxidized α-[SiW VI12O 40] 4- was crystallized with the neutral TTFPy moiety from the acetonitrile solution because of the low electron-withdrawing ability of α-[SiW VI12O 40] 4-, forming a brown-orange crystal. The crystal colour quickly turned to black by immersing in methanol, due to CT from TTF moiety to α-[SiW VI12O 40] 4-, which was caused by the solvent effect. Increase in the solvent acceptor number from 18.9 for acetonitrile to 41.3 for methanol resulted in the enhancement of the electron withdrawing ability of α-[SiW VI12O 40] 4- by 0.317 V in methanol. © 2012 The Royal Society of Chemistry.

    DOI: 10.1039/c2dt30398a

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  • Cation-anion packing and molecular motion in (m-fluoroanilinium) (dibenzo[18]crown-6)[Ni(mnt) <sub>2</sub>] <sup>-</sup>(CH <sub>3</sub>CN) <sub>0.25</sub> crystals 査読

    Kiyonori Takahashi, Norihisa Hoshino, Kazuya Kubo, Takayoshi Nakamura, Tomoyuki Akutagawa

    CrystEngComm   14 ( 16 )   5235 - 5241   2012年8月

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    掲載種別:研究論文(学術雑誌)  

    The hydrogen-bonding (m-fluoroanilinium)(dibenzo[18]crown-6) supramolecule was complexed with the monovalent [Ni(mnt) 2] - (mnt -2 = maleonitriledithiolate) anion and the crystal structure, thermal stability, and dielectric properties were investigated with respect to the motional freedom of m-fluoroanilinium (m-FAni +) in (m-FAni +)(dibenzo[18]crown-6)[Ni(mnt) 2] -·(CH 3CN) 0.25 (1). The π-planar [Ni(mnt) 2] - anions were stacked along the a-axis and the orientational disorder of fluorine atoms in the m-FAni + cation was observed by X-ray crystal structural analysis at 100 K. Thermogravimetry and differential scanning calorimetry analyses and dielectric constant measurements showed an anomaly at 360 K during the first heating process, where the CH 3CN molecule was released from the crystal while maintaining the block-shape of the single crystal. The cation-anion packing was compared with that of ferroelectric (m-FAni +)(dibenzo[18]crown-6)[Ni(dmit) 2] - (2) and ferromagnetic (m-FAni +)(dibenzo[18] crown-6)[CrMn(oxalate) 3]·(CH 3CN)(CH 3OH) (3). The orientational disorder of the F-sites of m-FAni + in crystal 1 was associated with the presence of the CH 3CN molecule, which was different from the two-fold flip-flop motion of m-FAni + in ferroelectric crystal 2. Potential energy calculations revealed asymmetric double minimum-type potential energy with energy barriers of 180 and 900 kJ mol -1. The cation-anion packing of crystal 1 was loose compared with that of crystals 2 and 3; therefore, the thermal stability of crystal 1 was lower than that of crystals 2 and 3. The two-dimensional anionic layer in crystals 2 and 3 enhanced the thermal stability of the crystals, whereas the one-dimensional π-stacking structure of anions in 1 decreased its thermal stability. © 2012 The Royal Society of Chemistry.

    DOI: 10.1039/c2ce25493j

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  • Crystal structures and magnetic properties of (4,4′-phenylazophenyl) diammonium(crown ethers)[Ni(dmit) <sub>2</sub>] <sub>2</sub> crystals 査読

    Norihisa Hoshino, Kazuya Kubo, Takayoshi Nakamura, Tomoyuki Akutagawa

    Dalton Transactions   41 ( 31 )   9297 - 9303   2012年8月

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    掲載種別:研究論文(学術雑誌)  

    Sandwich-type hydrogen-bonded supramolecular dications (DAAz 2+)([18]crown-6) 2 and (DAAz 2+) (dicyclohexane[18]crown-6) 2 (DAAz 2+ = 4,4′- (phenylazophenyl)diammonium) were introduced into [Ni(dmit) 2] - anions via a diffusion method to form novel single crystals (DAAz 2+)([18]crown-6) 2[Ni(dmit) 2] 2 (1) and (DAAz 2+)(dicyclohexane[18]crown-6) 2[Ni(dmit) 2] 2 (2), respectively, which were characterized based on their crystal structures and magnetic susceptibilities. The molecular assembly structures and its physical properties were expanded in the use of a three component molecular network system. The two ammonium groups (-NH 3+) of the DAAz 2+ dication formed N-H +-O hydrogen-bonding interactions with the oxygen atoms of [18]crown-6 and dicyclohexane[18]crown-6. In the case of crystal 1, an alternating π-stacking interaction was observed for the [Ni(dmit) 2] - anions, whereas orthogonal linear π-S interactions were detected for crystal 2. Temperature-dependent magnetic susceptibilities of crystals 1 and 2 followed the alternate Heisenberg antiferromagnetic chain (J = -15.8 K) and linear Heisenberg antiferromagnetic chain (J = -13.7 K) models, respectively. © 2012 The Royal Society of Chemistry.

    DOI: 10.1039/c2dt30807j

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  • A light-induced phase exhibiting slow magnetic relaxation in a cyanide-bridged [Fe <sub>4</sub>Co <sub>2</sub>] complex 査読

    Masayuki Nihei, Yuki Okamoto, Yoshihiro Sekine, Norihisa Hoshino, Takuya Shiga, Isiah Po Chun Liu, Hiroki Oshio

    Angewandte Chemie - International Edition   51 ( 26 )   6361 - 6364   2012年6月

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    掲載種別:研究論文(学術雑誌)  

    Single-molecule magnets: A cyanide-bridged hexanuclear complex showed a thermal electron-transfer-coupled spin transition centered at 220a K. Light irradiation at low temperature (LT; HT=high temperature) generated a metastable state showing slow magnetic relaxation in measurements of the alternating-current magnetic susceptibility (Ï m; see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/anie.201202225

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  • Huge dielectric response and molecular motions in paddle-wheel [Cu <sup>II</sup><sub>2</sub>(Adamantylcarboxylate) <sub>4</sub>(DMF) <sub>2</sub>]a·(DMF) <sub>2</sub> 査読

    Qiong Ye, Kiyonori Takahashi, Norihisa Hoshino, Takemitsu Kikuchi, Tomoyuki Akutagawa, Shin Ichiro Noro, Sadamu Takeda, Takayoshi Nakamura

    Chemistry - A European Journal   17 ( 51 )   14442 - 14449   2011年12月

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    掲載種別:研究論文(学術雑誌)  

    The temperature-dependent dynamic properties of [Cu II2(ADCOO) 4(DMF) 2]â(DMF) 2 (1) and [Cu II2(ADCOO) 4(AcOEt) 2] (2) crystals were examined by X-ray crystallography, 1H NMR spectroscopy, and measurements of the dielectric constants and magnetic susceptibilities (ADCOO=adamantane carboxylate, DMF=N,N-dimethylformamide, and AcOEt=ethyl acetate). In both crystals, four ADCOO groups bridged a binuclear Cu II-Cu II bond, forming a paddle-wheel [Cu II2(ADCOO) 4] structure. The oxygen atoms of two DMF molecules in crystal 1 and two AcOEt molecules in crystal 2 were coordinated at axial positions of the [Cu II2(ADCOO) 4] moiety, forming [Cu II2(ADCOO) 4(DMF) 2] and [Cu II2(ADCOO) 4(AcOEt) 2], respectively. Two additional DMF molecules were included in the unit cell of crystal 1, whereas AcOEt was not included in the unit cell of crystal 2. The structural analyses of crystal 1 at 300 K showed three-fold rotation of the adamantyl groups, whereas rotation of the adamantyl groups of crystal 2 at 300 K was not observed. Thermogravimetric measurements of crystal 1 indicated a gradual elimination of DMF upon increasing the temperature above 300 K. The dynamic behavior of the crystallized DMF yielded significant temperature-dependent dielectric responses in crystal 1, which showed a huge dielectric peak at 358 K in the heating process. In contrast, only small frequency-dependent dielectric responses were observed in crystal 2 because of the freezing of the molecular rotation of the adamantyl groups. The magnetic behavior was dominated by the strong antiferromagnetic coupling between the two S=1/2 spins of the Cu II-Cu II site, with magnetic exchange energies (J) of -265 K (crystal 1) and -277 K (crystal 2). © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/chem.201101743

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  • Polymorphs and structural phase transition of [Ni(dmit)<sub>2</sub>] <sup>-</sup> crystals induced by flexible (trans -cyclohexane-1,4-diammonium) (benzo[18]crown-6)<sub>2</sub> supramolecule 査読

    Qiong Ye, Tomoyuki Akutagawa, Norihisa Hoshino, Takemitsu Kikuchi, Shin Ichiro Noro, Ren Gen Xiong, Takayoshi Nakamura

    Crystal Growth and Design   11 ( 9 )   4175 - 4182   2011年9月

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    掲載種別:研究論文(学術雑誌)  

    Structurally flexible trans-cyclohexane-1,4-diammonium (CHDA2+) forms a hydrogen-bonded sandwich-type supramolecule with benzo[18]crown-6 in (CHDA2+)(benzo[18]crown-6)2[Ni(dmit)2] 2 (1) (dmit2-: 2-thioxo-1,3-dithiole-4,5-dithiolate). During the crystallization, the three crystal polymorphs 1a, 1b, and 1c were obtained in the space groups P21/c, P1̄, and P1̄, in which the orientation of the benzene rings of benzo[18]crown-6 in the sandwich-type supramolecular cations and the [Ni(dmit)2]- arrangements were different. Crystal 1c had a structural phase transition at ∼200 K, at which the unit cell volume of the low-temperature phase (1d) became twice that of the high-temperature phase (1c). The [Ni(dmit)2] π-dimer was observed in crystals 1a, 1b, 1c, and 1d. A double-minimum-type potential energy profile was observed for the rigid rotation of CHDA2+ around the N-N axis. Among four new crystals, the relatively low potential energy barrier of ∼120 kJ mol-1 for crystal 1b was consistent with the temperature- and frequency-dependent dielectric constants. The crystal polymorph and structural phase transition were coupled in (CHDA2+)(benzo[18]crown- 6)2[Ni(dmit)2]-2. © 2011 American Chemical Society.

    DOI: 10.1021/cg2007556

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  • Achiral single molecule magnet and chiral single chain magnet 査読

    Norihisa Hoshino, Yoshihiro Sekine, Masayuki Nihei, Hiroki Oshio

    Chemical Communications   46 ( 33 )   6117 - 6119   2010年9月

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    掲載種別:研究論文(学術雑誌)  

    An achiral molecular square and a chiral chain composed of cyanide bridged FeIII and NiII ions were prepared, and they act as a single molecule magnet and a chiral single chain magnet, respectively. © 2010 The Royal Society of Chemistry.

    DOI: 10.1039/c0cc00184h

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  • Contrasting magnetism of [Mn<sub>2</sub><sup>III</sup>] and [Mr <sub>2</sub><sup>II</sup>Mn<sub>2</sub><sup>III</sup>] squares 査読

    Takuto Matsumoto, Takuya Shiga, Mao Noguchi, Tatsuya Onuki, Graham N. Newton, Norihisa Hoshino, Motohiro Nakano, Hiroki Oshio

    Inorganic Chemistry   49 ( 2 )   368 - 370   2010年1月

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    掲載種別:研究論文(学術雑誌)  

    Two tetranuclear manganese distorted square-shaped clusters, [Mn 4III(L1)4(μ2-OMe)4] · 2.5H2O (1)and [Mn2IIMn 2III(L2)4(H2O)2]-(PF 6)2·CHCl3-CH3OH-1.5H 2O (2) (H2L1 = 2-[3-(2-hydroxyphenyl)-1H-pyrazol-5-yl]-6- pyridinecarboxylic acid methyl ester; H2L2 = 2-[3-(2-hydroxyphenyl)- 1H-pyrazol-5-yl]-6-pyrldinecarboxylic acid ethyl ester), exhibit antiferromagnetic and ferromagnetic interactions between neighboring manganese ions, respectively. © 2009 American Chemical Society.

    DOI: 10.1021/ic902052f

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  • Cobalt antiferromagnetic ring and grid single-molecule magnet 査読

    Takuya Shiga, Takuto Matsumoto, Mao Noguchi, Tatsuya Onuki, Norihisa Hoshino, Graham N. Newton, Motohiro Nakano, Hiroki Oshio

    Chemistry - An Asian Journal   4 ( 11 )   1660 - 1663   2009年11月

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    掲載種別:研究論文(学術雑誌)  

    Grid magnet: A Co8 ring and a Co9 grid complex are synthesized using a multidentate polypyridine-type ligand and are shown to exhibit all antiferro-magnetic interactions between metal Grid magnet: A Co8 ring and a Co9 grid complex are synthesized using a multidentate polypyridine-type ligand and are shown to exhibit all antiferro-magnetic interactions between metal centers, with the grid complex displaying SMM properties as a result of alternating high spin/low spin metal centers in the outer 8-membered ring. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

    DOI: 10.1002/asia.200900216

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  • Templating odd numbered magnetic rings: Oxovanadium heptagons sandwiched by β-cyclodextrins 査読

    Norihisa Hoshino, Motohiro Nakano, Hiroyuki Nojiri, Wolfgang Wernsdorfer, Hiroki Oshio

    Journal of the American Chemical Society   131 ( 42 )   15100 - 15101   2009年10月

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    掲載種別:研究論文(学術雑誌)  

    (Graph Presented) The oxovanadium heptagons sandwiched by β-cyclodextrins showed stepped magnetization curves, which were characteristic of level crossings of spin sublevels. Doubly degenerate ground Kramers' doublets split into two spin states, and the splitting energy gaps depend upon ring distortions. © 2009 American Chemical Society.

    DOI: 10.1021/ja9066496

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  • Chiral dinuclear complexes with tetradentate ligands derived from (R)-(+)-1, 1′-binaphthyl-2,2′-diamine 査読

    Norihisa Hoshino, Takuya Shiga, Masayuki Nihei, Hiroki Oshio

    Polyhedron   28 ( 9-10 )   1754 - 1757   2009年6月

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    掲載種別:研究論文(学術雑誌)  

    Novel chiral dinuclear complexes of Δ, Δ - [Ni2II ((R) -Hsalbn) ((R) -salbn) (MeCN)2] (ClO4) · 2 MeCN (1) and Λ, Λ - [Fe2III ((R) -salbn)2 (OMe)2] · Et2 O · H2 O (2) ((R)-H2salbn = N,N′-disalicylidene-(R)-1,1′-binaphthyl-2,2′-diaminate) were prepared. X-ray crystal structure analyses revealed that both complexes crystallized in chiral space groups of P212121 and P41212, respectively. In 1, two Ni(II) ions with Δ configuration are bridged by phenoxo groups of (R)-salbn, while in 2 μ2-methoxo ions bridge two Fe(III) ions leading to the Λ absolute configuration. Dc magnetic susceptibility measurements suggested antiferromagnetic interactions operative in 1 and 2. © 2008 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.poly.2008.11.029

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  • Molecular magnets containing wheel motifs 査読

    Norihisa Hoshino, Ayuk M. Ako, Annie K. Powell, Hiroki Oshio

    Inorganic Chemistry   48 ( 8 )   3396 - 3407   2009年4月

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    掲載種別:研究論文(学術雑誌)  

    An overview of some compounds with structures that can be regarded as derived from an {Fe7(μ3-OR)6(μ-OR)6} motif is presented. Many of these compounds act as single-molecule magnets. In addition, the results of a comprehensive study on the single-crystal structures, magnetism, and spin structures for five new iron compounds with structural components related to this are given. This serves to illustrate the methodology that can be used to unravel the complicated magnetic behavior of such systems. Thus, the alkoxo- and phenoxo-bridged multinuclear iron complexes, [Fe II7(Hbmsae)6(OMe)6]C l2.6H2O (6), [FeIIFeIII6(bmsae)6(μ3-OMe)6]C l2.23H2O (7), [NaFeIII6(bmsae) 6(μ3- OMe)6]Cl.30H2O (8), [Fe III3(bmsae)3Cl2(MeOH)(OMe)].MeOH.Et 2O (9), and [FeIII2(Hbmsae) 2(OMe)2Cl2][Fe3- (bmsae) 3(OMe)Cl2(MeOH)]2 . 1.5MeOH (10), were prepared by the reactions of iron sources with Schiff base ligands (H2bmsae ) 5-bromo-3-methoxysalicylideneaminoethanol). Heptanuclear complexes of 6 and 7 have wheel structures in which six iron(II) and six iron(III) ions locate on the rim with the central iron(II) ions, respectively, while 8 also has a wheel structure with a diamagnetic sodium ion in the center. 9 is a trinuclear ferric complex with an incomplete cubic structure. In 10, di- and trinuclear complexes exist in the crystal, where the trinuclear complex has an incomplete cubic structure similar to that of 9. Magnetic susceptibility measurements revealed that 6 has an S ) 10 spin ground state, while the antiferromagnetic interactions dominate in 7-10. © 2009 American Chemical Society.

    DOI: 10.1021/ic801776w

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  • Undecanuclear mixed-valence 3d-4f bimetallic clusters 査読

    Takuya Shiga, Tatsuya Onuki, Takuto Matsumoto, Hiroyuki Nojiri, Graham N. Newton, Norihisa Hoshino, Hiroki Oshio

    Chemical Communications   ( 24 )   3568 - 3570   2009年

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    掲載種別:研究論文(学術雑誌)  

    Two undecanuclear 3d-4f clusters with the general formula {Mn III4MnIVLnIII6}, where Ln = Gd or Tb, were synthesized, with both showing large spin ground states, and the Tb species acting as a single molecule magnet. © 2009 The Royal Society of Chemistry.

    DOI: 10.1039/b905480d

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  • Syntheses, structures, and magnetic properties of manganese-lanthanide hexanuclear complexes 査読

    Takuya Shiga, Norihisa Hoshino, Motohiro Nakano, Hiroyuki Nojiri, Hiroki Oshio

    Inorganica Chimica Acta   361 ( 14-15 )   4113 - 4117   2008年10月

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    掲載種別:研究論文(学術雑誌)  

    Reactions of manganese acetate and lanthanide acetate with Schiff-base ligands (H3beemp = 2,6-bis[((2-(2-hydroxyethoxy)ethyl)imino)methyl]-4-methylphenol) yielded hexanuclear clusters of [Mn4III Ln2III(μ3-O)2(Hbeemp)2(OAc)8(μ3-OMe)2(H2O)2] · C8H17OH (Ln = Gd, Tb, and Y for 1, 2, and 3, respectively). Magnetic susceptibility measurements revealed that the mixed spin systems of 1 and 2 showed ferrimagnetic behavior, while antiferromagnetic interactions were operative among Mn3+ ions in 3. Ac magnetic susceptibility measurements for 2 showed frequency dependent in- and out-of-phase signals, confirming slow magnetic relaxation of spin reorientations. © 2008 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.ica.2008.03.096

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  • Cyanide-bridged iron(II,III) cube with multistepped redox behavior 査読

    Masayuki Nihei, Mayumi Ui, Norihisa Hoshino, Hiroki Oshio

    Inorganic Chemistry   47 ( 14 )   6106 - 6108   2008年7月

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    掲載種別:研究論文(学術雑誌)  

    A building unit of Prussian blue was isolated as a cyanide-bridged iron cube of [FeII4FeIII4(CN) 12(tp)8]·12DMF·2Et2O· 4H2O [tp- = hydrotris(pyrazolyl)borate]. A cyclic voltammogram showed quasi-reversible four-stepped redox waves, which correspond to [FeIII4FeII4]/[Fe III5FeII3]+, [Fe III5FeII3]+/[Fe III6FeII2]2+, [Fe III6FeII2]2+/[Fe III7FeII1]3+, and [FeIII7FeII1]3+/[Fe III8]4+ processes. Controlled potential absorption spectral measurements revealed two intervalence charge-transfer bands at 816 and 1000 nm, which were assigned to charge transfers from Fe II ions to adjacent and remote FeIII ions, respectively, in the cube. © 2008 American Chemical Society.

    DOI: 10.1021/ic7024582

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  • A novel octanuclear manganese cluster with [Mn<sup>II</sup><sub>4</sub>(μ<sub>4</sub>-O)] core 査読

    Takuya Shiga, Lingqin Han, Masayuki Nihei, Norihisa Hoshino, Tasuku Ito, Hiroki Oshio

    Chemistry Letters   35 ( 4 )   440 - 441   2006年4月

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    掲載種別:研究論文(学術雑誌)  

    The reaction of MnCl2·4H2O with 2-aminoethanethiol (= Haet) under anaerobic conditions afforded yellow plate crystals of octanuclear manganese complex [Mn4(μ4-O) (Mn(aet)3}4]Cl2·MeOH·4H 2O. A complex molecule consists of four fac(S)-[Mn(aet)3] units linked to MnII4(μ4-O) core by thiolato bridges. Magnetic susceptibility measurements revealed the presence of antiferromagnetic interactions through μ4-oxo and μ2-thiolato bridges. Copyright © 2006 The Chemical Society of Japan.

    DOI: 10.1246/cl.2006.440

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  • Single-molecule magnets of ferrous cubes: Structurally controlled magnetic anisotropy 査読

    Hiroki Oshio, Norihisa Hoshino, Tasuku Ito, Motohiro Nakano

    Journal of the American Chemical Society   126 ( 28 )   8805 - 8812   2004年7月

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    掲載種別:研究論文(学術雑誌)  

    Tetranuclear FeII cubic complexes were synthesized with Schiff base ligands bridging the FeII centers. X-ray structural analyses of six ferrous cubes, [Fe4(sap)4(MeOH)4] ·2H2O (1), [Fe4(5-Br-sap)4-(MeOH) 4] (2), [Fe4(3-MeO-sap)4(MeOH) 4]·2MeOH (3), [Fe4(sae)4(MeOH) 4] (4), [Fe4(5-Br-sae)4(MeOH) 4]· MeOH (5), and [Fe4(3,5-Cl2-sae) 4(MeOH)4] (6) (R-sap and R-sae were prepared by condensation of salicylaldehyde derivatives with aminopropyl alcohol and aminoethyl alcohol, respectively) were performed, and their magnetic properties were studied. In 1-6, the alkoxo groups of the Schiff base ligands bridge four FeII ions in a μ3-mode forming [Fe4O 4] cubic cores. The Fell ions in the cubes have tetragonally elongated octahedral coordination geometries, and the equatorial coordination bond lengths in 4-6 are shorter than those in 1-3. Dc magnetic susceptibility measurements for 1-6 revealed that intramolecular ferromagnetic interactions are operative to lead an S = 8 spin ground state. Analyses of the magnetization data at 1.8 K gave the axial zero-field splitting parameters (D) of +0.81, +0.80, +1.15, -0.64, -0.66, and -0.67 cm-1 for 1-6, respectively. Ac magnetic susceptibility measurements for 4-6 showed both frequency dependent in- and out-of-phase signals, while 1-3 did not show out-of-phase signals down to 1.8 K, meaning 4-6 are single-molecule magnets (SMMs). The energy barriers to flip the spin between up- and down-spin were estimated to 28.4, 30.5, and 26.2 K, respectively, for 4-6. The bridging ligands R-sap2- in 1-3 and R-sae2- in 4-6 form six- and five-membered chelate rings, respectively, which cause different steric strain and Jahn-Teller distortions at FeII centers. The sign of the D value was discussed by using angular overlap model (AOM) calculations for irons with different coordination geometry.

    DOI: 10.1021/ja0487933

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  • Structures and magnetic properties of metal cubes 査読

    Masayuki Nihei, Norihisa Hoshino, Tasuku Ito, Hiroki Oshio

    Polyhedron   22 ( 14-17 )   2359 - 2362   2003年7月

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    掲載種別:研究論文(国際会議プロシーディングス)  

    Structures and magnetic properties of copper(II), nickel(II) and manganese(II) cubes are presented. In the cubes, four metal ions are assembled into the cubes by tridentate Schiff base ligands. Magnetic succeptibility measurements revealed the copper and nickel cubes have high-spin ground state, while the manganese cube has a S = 0 spin ground state. © 2003 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0277-5387(03)00159-1

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  • Multinculear nickel(II) complexes with Schiff base ligands 査読

    Norihisa Hoshino, Tasuku Ito, Masayuki Nihei, Hiroki Oshio

    Synthetic Metals   137 ( 1-3 )   1309 - 1310   2003年4月

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    掲載種別:研究論文(国際会議プロシーディングス)  

    The crystal structure and magnetic properties of dinuclear and tetranuclear Ni(II) complexes with Schiff base ligands were investigated. Nickel(II) ions were coordinated by one nitrogen and five oxygen atoms from methanol, acetate, and monoanionic Schiff base. Results showed the structure contained a tetranuclear cubane core, of which four nickel(II) ions were bridged by μ3-alkoxo groups.

    DOI: 10.1016/S0379-6779(02)00994-3

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  • Syntheses, structures and magnetic properties of multinuculear manganese complexes with Schiff base ligands 査読

    Norihisa Hoshino, Tasuku Ito, Masayuki Nihei, Hiroki Oshio

    Inorganic Chemistry Communications   6 ( 4 )   377 - 380   2003年4月

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    掲載種別:研究論文(学術雑誌)  

    Multinulear manganese complexes with Schiff base ligands, [{Mn4III(μ3-O) (sae)4(μ-N3) (CH3OH)}2(μ-N3)]N3 ([1]N3), [Mn6III (μ3-O)2(sae)6(NCS)2] (2) and [Mn4IIMn2III (sae)6(CH3OH)2Cl2] (3) (H2sae = 2-salicylideneaminoethanol), were prepared and the crystal structures and magnetic properties were studied. © 2002 Elsevier Science B.V. All rights reserved.

    DOI: 10.1016/S1387-7003(02)00793-1

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  • High-spin wheel of a heptanuclear mixed-valent Fe<sup>II,III</sup> complex 査読

    Hiroki Oshio, Norihisa Hoshino, Tasuku Ito, Motohiro Nakano, Franz Renz, Philipp Gütlich

    Angewandte Chemie - International Edition   42 ( 2 )   223 - 225   2003年1月

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    掲載種別:研究論文(学術雑誌)  

    Wheels with high spins: The reaction of a tridentate Schiff base ligand with iron (II) chloride, and subsequent oxidation with [(tBu4N) MnO4] yielded a heptanuclear mixed-valent iron wheel (see picture) with a spin ground state of S = 29/2. Cornering the 13th vertex: The first 13-vertex carborane (see picture, B: brown, C: gray, H: white) has been prepared by a methodology that can in principle be applied repeatedly, leading to 14-, 15-, 16-, ... vertex carboranes in the future. The 13-vertex species has a henicosahedral geometry, not the docosahedral one expected, but the two forms are found to be very close in energy by DFT calculations.

    DOI: 10.1002/anie.200390084

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  • Incomplete and complete manganese cubes 査読

    Masayuki Nihei, Norihisa Hoshino, Tasuku Ito, Hiroki Oshio

    Chemistry Letters   ( 10 )   1016 - 1017   2002年10月

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    掲載種別:研究論文(学術雑誌)  

    Reactions of MnCl2·4H2O with 2-(5-bromo salicylideneamino)-1-propanol (H2(5-Br-sap)) under aerobic conditions and with 2-salicylideneamino-1-propanol (H2(sap)) under strict anaerobiosis yielded tri and tetranuclear manganese complexes of [MnIII3(μ3-O)(5-Br-sap)3(H 2O)3]Cl·5.5H2O (1) and [MnII4(sap)4(MeOH)4]·2H 2O (2), respectively; the magnetic susceptibility measurements revealed intramolecular antiferromagnetic interactions being operative in both compounds, of which exchange coupling constant for 2 was estimated to be -1.6 cm-1 (H = -2JΣSi·Sj).

    DOI: 10.1246/cl.2002.1016

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  • Structures and magnetic properties of di and tetranuclear nickel(II) complexes with schiff base ligands 査読

    Norihisa Hoshino, Tasuku Ito, Masayuki Nihei, Hiroki Oshio

    Chemistry Letters   ( 8 )   844 - 845   2002年8月

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    掲載種別:研究論文(学術雑誌)  

    Reactions of Ni(CH3COO)2·4H2O and NiCl2·6H2O with Schiff base ligands yielded di and tetranuclear nickel(II) complexes of [Ni2(Hhsae)2(CH3COO)2(MeOH) 2] (1) and [Ni4(sae)4(MeOH)4] (2) (H2sae = 2-(5-hydroxysalicylideneamino)ethanol and H2sae = 2-salicylideneaminoethanol). Magnetic susceptibility measurements revealed that 1 and 2 have singlet and nonet spin ground states, respectively.

    DOI: 10.1246/cl.2002.844

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  • Ferromagnetic interactions in metal complexes with imino nitroxides 査読

    H. Oshio, M. Yamamoto, N. Hoshino, T. Ito

    Polyhedron   20 ( 11-14 )   1621 - 1625   2001年5月

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    掲載種別:研究論文(国際会議プロシーディングス)  

    Copper(II), nickel(II), and zinc(II) complexes with tridentate imino nitroxyl diradicals, [CuCl(bisimpy)(MeOH)](PF6) (1), [NiCl(bisimpy)(H2O)2]Cl·2H2O (2), and [ZnCl2(bisimpy)] (3) (bisimpy = 2,6-bis(1′-oxyl-4′,4′,5′,5′-tetramethyl- 4′,5′-dihydro-1′H-imidazol-2′-yl)pyridine), were prepared and their magnetic properties studied. In 1-3 the diradicals are ferromagnetically coupled with the inter-radical coupling constant of J = + 6.5 cm-1. In 1 and 2 the ferromagnetic interactions between the paramagnetic metal ions and the coordinated imino nitroxides are operative with the J values of + 165 and + 120 cm-1 (H = -2JijΣSiSj), respectively. Magnetic properties of a Cu(II) complex with a mono radical ligand, [CuCl2(impy)] (4) (impy = 2-(1′-oxyl-4′,4′,5′,5′tetramethyl- 4′,5′-dihydro-1′H-imidazol-2′-yl)pyridine), were also studied; a ferromagnetic coupling constant of J = + 50(2) cm-1 was obtained. © 2001 Elsevier Science Ltd.

    DOI: 10.1016/S0277-5387(01)00663-5

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  • Superparamagnetic behavior in an alkoxo-bridged iron(II) cube 査読

    H. Oshio, N. Hoshino, T. Ito

    Journal of the American Chemical Society   122 ( 50 )   12602 - 12603   2000年12月

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講演・口頭発表等

  • 水素結合性強誘電結晶の相転移に伴う熱伝導度の変化

    星野哲久; 芥川智行

    日本化学会第100春季年会  2020年3月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • Variations of thermal conductivities in the sequential phase transitions of the two-dimensional tetrachlorocupric salt

    星野哲久, 田村駿作, 芥川智行

    錯体化学会第69回討論会  2019年9月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • Magnetism and redox properties of the trinuclear iron(III) complex with the redox-active triangular conjugated bridge 国際会議

    星野哲久, 芥川智行

    International Conference on Coordination Chemistry (ICCC2018)  2018年8月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • Intramolecular electron transfer of a trinuclear iron(III) complex with a triangular radical cation conjugate bridge

    星野哲久, 芥川智行

    錯体化学第67回討論会  2017年9月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • 酸化還元活性なトリフェニレン誘導体を配位子にもつ鉄三核錯体の合成

    星野哲久, 芥川智行

    日本化学会第97春季年会  2017年3月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • 水素結合ネットワークをもつ有機強弾性結晶のプロトンダイナミクス 招待

    星野哲久

    日本化学会中国四国支部大会  2016年11月 

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    記述言語:日本語   会議種別:口頭発表(招待・特別)  

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  • Spin state transitions of trinuclear Iron(III) complexes with triphenylene-based templates 国際会議

    星野哲久, 芥川智行

    Workshop for Young Investigators on Functional Molecular Materials and Molecular Related Magnetism (Rising Star Pre-ICMM2016)  2016年9月 

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    記述言語:英語   会議種別:ポスター発表  

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  • Commensurate-Incommensurate Phase Transitions and Physical Properties of Layered Complexes of (CnH2n+1NH3)2CuCl4' 国際会議

    星野哲久

    4th HeKKSaGOn Presidents’ Conference  2015年4月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • キヌクリジン型分子ローターが配位した金属錯体の合成と物性

    星野哲久, 武田貴志, 芥川智行

    錯体化学会第64回討論会  2014年9月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • Phase Transitions and Dielectric Properties of Organic-Inorganic Layered Complexes of (CnH2n+1NH3)2CuCl4 国際会議

    星野哲久, 田村駿作, 芥川智行

    The 4th Asian Conference on Coordination Chemistry (ACCC2013)  2013年11月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • 点接触粘弾性イメージング原子間力顕微鏡の開発

    星野哲久, 芥川智行

    第7回分子科学討論会  2013年9月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • アダマンタン骨格をもつ極性有機分子を用いた薄膜作製と柔粘性相転移

    星野哲久

    日本化学会第93春季年会  2013年3月 

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  • Magnetism and dielectricity of molecular magnets with motional freedom 招待 国際会議

    星野哲久

    International Workshop on Development of Functionalized Molecule-based Magnetic Materials  2013年2月 

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  • 一置換アダマンチル基を配位子にもつパドルホイール型ルテニウム二核錯体の誘電緩和

    星野哲久

    錯体化学会第62回討論会  2012年9月 

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  • アザアダマンタン-N-オキシルラジカルの固体内分子運動

    星野哲久, 武田貴志, 芥川智行

    第6回分子科学討論会  2012年9月 

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  • Dielectric Anomalies of Single Molecule Magnets with Polar Rotational Ligands 国際会議

    星野哲久, 芥川智行

    The 40th International Conference on Coordination Chemistry (ICCC40)  2012年9月 

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  • Dielectric Relaxation of Single Molecule Magnets with Polar Rotational Ligands

    Norihisa Hoshino; Takashi Takeda; Tomoyuki Akutagawa

    KJF International Conference on Organic Materials for Electronics and Photonics 2012  2012年8月 

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  • アダマンタン骨格をもつ極性分子の結晶内分子運動と誘電性

    星野哲久; 武田貴志; 菊地毅光; 芥川智行

    東北大学多元物質科学研究所 高分子・ハイブリッド材料研究センター 2012 PHyMシンポジウム  2012年6月 

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  • アダマンタン骨格をもつ極性有機分子の結晶構造と誘電物性

    星野哲久; 武田貴志; 芥川智行

    日本化学会第92春季年会  2012年3月 

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  • 銅二核錯体結晶のアダマンチル基の分子回転と連動した巨大誘電応答

    星野哲久; 芥川智行

    新学術領域研究「分子自由度が拓く新物質科学」第6回領域会議  2012年1月 

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  • Mn12 Single Molecule Magnets with Polar Rotational Ligands 国際会議

    星野哲久, 芥川智行

    3rd Asian Conference on Coordination Chemistry (ACCC3)  2011年10月 

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  • マンガン12核単分子磁石への極性回転部位をもつ配位子の導入

    星野哲久, 芥川智行

    錯体化学会第61回討論会  2011年9月 

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  • 電子移動反応を示すシアン化物イオン架橋一次元錯体

    星野哲久, 吉田典史, 志賀拓也, 二瓶雅之, 大塩寛紀

    日本化学会第91春季年会  2011年3月 

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  • Control in structure and physical property of (Li+ or Na+)(crown ether)TCNQ complexes by size matching between metal cations and crown ethers

    令和2年度化学系学協会東北大会  2020年9月 

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  • Preparation and molecular assembly of tribenzodehydroannulenes with octylcarboxylphenyl groups

    令和2年度化学系学協会東北大会  2020年9月 

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  • Synthesis and physical property of amphiphilic oligo(ethyleneglycol) derivatives

    瀬戸信弥; 芥川智行; 武田貴志; 星野哲久

    令和2年度化学系学協会東北大会  2020年9月 

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  • Elastic deformation and crystal structures of the halogenated anthracene single crystals

    趙宇軒; 星野哲久; 武田貴志; 林祥太郎; 芥川智行

    令和2年度化学系学協会東北大会  2020年9月 

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  • Ferroelectric low-voltage ON/OFF switching of chiral-alkylamide substituted benzene derivative

    呉 筧筠; 武田 貴志; 星野 哲久; 芥川 智行

    令和2年度化学系学協会東北大会  2020年9月 

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  • 磁性薄膜エッジを利用したNi78Fe22/Mq3(M=Al; Er)/Ni78Fe22ナノ接合素子の電気磁気特性

    千秋賀英子; 佐々木悠馬; 中山雄介; 三澤貴浩; 小峰啓史; 星野哲久; 芥川智行; 藤岡正弥; 西井準治; 海住 英生

    日本物理学会 2020年秋季大会  2020年9月 

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  • 中性‐イオン性転移物質TTF-CAの熱伝導度測定

    竹原陵介; 堀内佐智雄; 西野智昭; 星野哲久; 芥川智行; 庄子良晃; 福島孝典

    第1回東北大学材料ウエビナー  2020年9月 

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  • オクチルカルボキシルフェニル基を有する、C3対称性デヒドロベンゾアヌレン類の集積構造と物性

    笠原遥太郎; 武田貴志; 星野哲久; 久木一朗; 芥川智行

    第14回分子科学討論会2020  2020年9月 

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  • 水の吸脱着に伴う電子移動度スイッチングを示すナフタレンジイミド誘導体

    阿部春花; 川崎渉; 武田貴志; 星野哲久; 松田若菜; 関修平; 芥川智行

    第14回分子科学討論会2020  2020年9月 

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  • M+ (クラウンエーテル)-TCNQ錯体の構造・物性に対するアルカリ金属とクラウンエーテルのサイズ効果

    三部宏平; 星野哲久; 武田貴志; 中村貴義; 芥川智行

    第14回分子科学討論会2020  2020年9月 

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  • Strain-stress curves and crystal structures of flexible halogenated anthracene crystals

    第14回分子科学討論会2020  2020年9月 

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  • Supramolecular assembly and dielectric response of alkylamide-substituted azobenzene derivatives

    第14回分子科学討論会2020  2020年9月 

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  • イソフタルアルキルアミド誘導体の誘電物性におよぼす置換基効果

    溝上諒平; 川名萌枝子; 武田貴志; 星野哲久; 芥川智行

    第14回分子科学討論会2020  2020年9月 

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  • 両親媒性ペンタエチレングリコール誘導体が形成するNa+錯体の構造と物性

    瀬戸信弥; 武田貴志; 星野哲久; 芥川智行

    第14回分子科学討論会2020  2020年9月 

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  • Elastic Deformation and Crystal Structures of The Halogenated Anthracene Single Crystals

    日本化学会第100春季年会  2020年3月 

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  • Ferroelectricity and Supramolecular Assembly of Chiral Alkyalmide Substituted Benzene Derivative

    日本化学会第100春季年会  2020年3月 

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  • Characterization of x-Li(Mc) radical crystal having one-dimensional channels

    日本化学会第100春季年会  2020年3月 

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  • ナフタレンジイミドジプロピオネート・アルカリ金属塩における水の吸脱着挙動を利用した有機半導体特性の制御

    阿部 春花; 川崎 渉; 武田 貴志; 星野 哲久; 松田 若菜; 関 修平; 芥川 智行

    日本化学会第100春季年会  2020年3月 

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  • Pyridinium誘導体/crown ether超分子カチオンを導入した[Ni(dmit)2]塩の構造と熱挙動

    高橋 仁徳; 土井 雄登; 星野 哲久; 久木 一朗; 芥川 智行; 中村 貴義

    日本化学会第100春季年会  2020年3月 

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  • Na+-(Crown Ether)-TCNQ錯体の構造と物性に及ぼす環サイズの効果

    三部 宏平; 星野 哲久; 武田 貴志; 中村 貴義; 芥川 智行

    日本化学会第100春季年会  2020年3月 

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  • DABCOとジアニオン性NDIからなるカチオン-アニオン塩の分子集合構造と物性

    川崎 渉; 武田 貴志; 星野 哲久; 松田 若菜; 関 修平; 芥川 智行

    日本化学会第100春季年会  2020年3月 

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  • ジアルキルアミド鎖を導入したオリゴ(エチレングリコール)誘導体の合成と物性

    瀬戸 信弥; 武田 貴志; 星野 哲久; 芥川 智行

    日本化学会第100春季年会  2020年3月 

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  • オクチルカルボニルフェニル基を有するヘキサデヒドロトリベンゾ[12]アヌレンの合成および物性

    笠原遥太郎; 武田貴志; 星野哲久; 久木一朗; 芥川智行

    日本化学会第100春季年会  2020年3月 

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  • lectric and magnetic properties in Ni78Fe22/Mq3 (M = Al; Er)/Ni78Fe22 nanoscale junction devices utilizing magnetic thin-film edges

    Yuma Sasaki; Robin Msiska; Takahiro Misawa; Sumito Mori; Takashi Komine; Norihisa Hoshino; Tomoyuki Akutagawa; Masaya Fujioka; Junji Nishii; Hideo Kaiju

    The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13)  2019年10月 

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  • High Temperature Ferroelectricity of Tetraphenylporphyrin Derivative Bearing -CONHC14H29 Chains

    Jianyun Wu; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    The 13rd Japan-China Joint Symposium on Conduction and Photoconduction in Organic Solids and Related Phenomena  2019年10月 

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  • A Correlation Between Cation Size and Electron Mobility in Dianionic Naphthalenediimide Derivatives

    Ayumi Kawasaki; Takashi Takeda; Norihisa Hoshino; Wakana Mastuda; Shu Seki; Tomoyuki Akutagawa

    The 13rd Japan-China Joint Symposium on Conduction and Photoconduction in Organic Solids and Related Phenomena  2019年10月 

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  • Crystal Structures and Electrical Properties of TCNQ Complexes with Li+(Crown Ether) Supramolecular Cations

    Kohei Sambe; Norihisa Hoshino; Takashi Takeda; Takayoshi Nakamura; Tomoyuki Akutagawa

    The 13rd Japan-China Joint Symposium on Conduction and Photoconduction in Organic Solids and Related Phenomena  2019年10月 

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  • Physical Properties of Cation-Anion Type Organic Semoconductor

    Ayumi Kawasakia; Norihisa Hoshino; Takashi Takeda; Wakana Matsuda; Shu Seki; Tomoyuki Akutagawa

    7TH ASIAN CONFERENCE ON COORDINATION CHEMISTRY (ACCC7)  2019年10月 

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  • Molecular Assembly and Electron Transport Properties of Naphthalenediimide Dipropionate Salts

    Haruka Abe; Ayumi Kawasaki; Takashi Takeda; Norihisa Hoshino; Wakana Matsuda; Shu Seki; Tomoyuki Akutagawa

    7TH ASIAN CONFERENCE ON COORDINATION CHEMISTRY (ACCC7)  2019年10月 

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  • Electronic Structure and Electrical Property of (Li+ or Na+)(Crown-Ether)TCNQ Complexes

    Kohei Sambe; Norihisa Hoshino; Takashi Takeda; Takayoshi Nakamura; Tomoyuki Akutagawa

    7TH ASIAN CONFERENCE ON COORDINATION CHEMISTRY (ACCC7)  2019年10月 

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  • Ferroelectricity and Even-Odd Effect of Terephthal-dialkylamide Derivatives

    Moeko Kawana; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    The 13th International Symposium on Crystalline Organic Metals; Superconductors and Magnets (ISCOM2019)  2019年9月 

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  • Nanoscale effect in mixed crystals between ferroelectric and antiferroelectric alkylamide-substituted benzene derivatives

    Jianyun Wu; Takashi Takeda; Norihisa Hoshino; Takayoshi Nakamura; Tomoyuki Akutagawa

    The 13th International Symposium on Crystalline Organic Metals; Superconductors and Magnets (ISCOM2019)  2019年9月 

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  • Correlation between electrical property and ionic motion in (Li+ or Na+)(Crown-Ether) -TCNQ complexes

    Kohei Sambe; Takashi Takeda; Norihisa Hoshino; Takayoshi Nakamura; Tomoyuki Akutagawa

    The 13th International Symposium on Crystalline Organic Metals; Superconductors and Magnets (ISCOM2019)  2019年9月 

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  • Chain-Length Dependent Electronic Transport Properties of Alkylammonium Salts with Dianionic Naphthalenediimide

    Ayumi Kawasaki; Takashi Takeda; Norihisa Hoshino; Wakana Matsuda; Shu Seki; Tomoyuki Akutagawa

    化学系学協会東北大会2019  2019年9月 

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  • Control in Molecular Assemblies and Electron Transport Properties of Alkali Metal Salts of Naphthalenediimide Derivative

    Haruka Abe; Takashi Takeda; Norihisa Hoshino; Wakana Matsuda; Shu Seki; Tomoyuki Akutagawa

    The 13th International Symposium on Crystalline Organic Metals; Superconductors and Magnets (ISCOM2019)  2019年9月 

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  • 強誘電性および反強誘電性アルキルアミド置換ベンゼン誘導体混晶の誘電応答

    呉 筧筠; 武田 貴志; 星野 哲久; 芥川 智行

    第13回分子化学討論会  2019年9月 

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  • テレフタルアルキルアミド誘導体の強誘電性と偶奇効果

    川名 萌枝子; 武田 貴志; 星野 哲久; 芥川 智行

    第13回分子化学討論会  2019年9月 

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  • 親水性トリエチレングリコール鎖を有するベンゼントリカルボキシ アミド誘導体の合成と物性

    靖 暁竹; 武田 貴志; 星野 哲久; 芥川 智行

    第13回分子化学討論会  2019年9月 

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  • ジアミノビチアゾールとリン酸からなる分子性結晶中の水素結合ネットワークとプロトン伝導

    原 国豪; 武田 貴志; 星野 哲久; 芥川 智行

    第13回分子化学討論会  2019年9月 

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  • ベンゾチアゾール誘導体の発光クロミズムを用いた酸性分子センサーの開発

    高橋 慧瑚; 武田 貴志; 星野 哲久; 坂井 賢一; 芥川 智行

    第13回分子化学討論会  2019年9月 

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  • (Li+ or Na+)(クラウンエーテル)超分子カチオンを含む導電性TCNQ錯体の動的構造と物性の相関

    三部 宏平; 星野 哲久; 武田 貴志; 中村 貴義; 芥川 智行

    第13回分子化学討論会  2019年9月 

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  • アルキルアンモニウム−ジアニオン性NDI塩のアルキル鎖長と電子移動特性の相関

    川崎 渉; 星野 哲久; 武田 貴志; 松田 若菜; 関 修平; 芥川 智行

    第13回分子化学討論会  2019年9月 

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  • ジアニオン性ナフタレンジイミド誘導体結晶の水の吸脱着と電子移動特性

    阿部 春花; 川崎 渉; 武田 貴志; 星野 哲久; 松田 若菜; 関 修平; 芥川 智行

    第13回分子化学討論会  2019年9月 

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  • (Li+ or Na+)(crown ether)-TCNQ錯体におけるイオンの動的挙動と電子物性

    三部宏平; 武田貴志; 星野哲久; 中村貴義; 芥川智行

    低次元系光機能材料研究会第8回サマーセミナー2019  2019年9月 

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  • 水の吸脱着と連動した電子移動度スイッチングを示すn型有機半導体材料の開発

    阿部春花; 川崎渉; 武田貴志; 星野哲久; 松田若菜; 関修平; 芥川智行

    低次元系光機能材料研究会第8回サマーセミナー2019  2019年9月 

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  • Modification of Mobile Ionic Environment and Electronic State of (Li+ or Na+)(Crown Ether)-TCNQ Salts

    Kohei Sambe; Norihisa Hoshino; Takashi Takeda; Takayoshi Nakamura; Tomoyuki Akutagawa

    Tohoku University's Chemistry Summer School 2018  2019年8月 

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  • Basic Benzothiazole Derivative for Sensing Material of Various Kinds of Acids

    Keigo Takahashi; Takashi Takeda; Norihisa Hoshino; Ken-ichi Sakai; Tomoyuki Akutagawa

    Tohoku University's Chemistry Summer School 2018  2019年8月 

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  • Functional Naphthalenediimide Derivatives with n-type Semiconductor Behavior

    Haruka Abe; Ayumi Kawasaki; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    Tohoku University's Chemistry Summer School 2018  2019年8月 

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  • Experimental and Theoretical Study on Tunnel Magnetocapacitance in Fe/MgF2 Nanogranular Films

    Robin MSISKA; Shusaku HONJO; Yuki ASAI; Masashi ARITA; Atsushi TSURUMAKI-FUKUCHI; Yasuo TAKAHASHI; Norihisa HOSHINO; Tomoyuki AKUTAGAWA; Osamu KITAKAMI; Masaya FUJIOKA; Junji NISHII; Hideo KAIJU

    6th Japan-Korea International Symposium on Materials Science and Technology 2019,  2019年8月 

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  • Semiconducting Properties of Alkylammonium salts of Dianionic Naphthalendiimide

    Ayumi Kawasaki; Norihisa Hoshino; Takashi Takeda; Wakana Matsuda; Shu Seki; Tomoyuki Akutagawa

    The 18th International Symposium on Novel Aromatic Compounds (ISNA-18)  2019年7月 

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  • Two-Dimensional Ferroelectrics of Helicene Derivative

    Hayato Anetai; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    The 18th International Symposium on Novel Aromatic Compounds (ISNA-18)  2019年7月 

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  • Phase Transition and Ferroelectricity of Hydrogen Bonded Porphyrin Derivative

    Jianyun Wu; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    The 18th International Symposium on Novel Aromatic Compounds (ISNA-18)  2019年7月 

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  • Fluorescent Chromic Pyridyl Benzothiazole Derivative for Acid Sensing

    Keigo Takahashi; Yuta Nakane; Takashi Takeda; Norihisa Hoshino; Ken-ichi Sakai; Tomoyuki Akutagawa

    The 18th International Symposium on Novel Aromatic Compounds (ISNA-18)  2019年7月 

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  • Reversible Channel-Layer Structural Transformation of Hydrogen-Bonding Bis-Urea Macrocycle

    Guohao Yuan; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    14th International Symposium on Macrocyclic and Supramolecular Chemistry  2019年6月 

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  • Preparations; Molecular Assemblies; and Physical Properties of Benzenecarboxamides Bearing Hydrophobic -CONHC10H21 Chains and Hydrophilic −CONH(CH2CH2O)3CH3 Chains

    JING; Xiaozhu; TAKEDA; Takashi; HOSHINO; Norihisa; AKUTAGAWA; Tomoyuki

    日本化学会第99回春季年会  2019年3月 

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  • テレフタルジアルキルアミド誘導体の強誘電性と偶奇効果

    川名萌枝子; 武田貴志; 星野哲久; 芥川智行

    日本化学会第99回春季年会  2019年3月 

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  • Dibenzo[24]crown-8/1-ethyl-3-methylimidazolium 超分子カチオンを導入した[Ni(dmit)2] アニオンラジカル塩の融解挙動と電気物性

    高橋仁徳; 白川祐基; 星野哲久; 野呂真一郎; 芥川智行; 中村貴義

    日本化学会第99回春季年会  2019年3月 

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  • ナフタレンジイミドジプロピオレートアルカリ金属塩の構造と物性

    阿部春花; 武田貴志; 星野哲久; 芥川智行

    日本化学会第99回春季年会  2019年3月 

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  • Molecular Assembly Structures and Dielectric Response of Mixed Crystals of Ferroelectric and Antiferroelectric Alkylamide-Substituted Benzene Derivatives

    WU; Jianyun; TAKEDA; Takashi; HOSHINO; Norihisa; AKUTAGAWA; Tomoyuki

    日本化学会第99回春季年会  2019年3月 

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  • Li+(Crown ether)−TCNQ 錯体の構造と電気物性

    三部宏平; 星野哲久; 武田貴志; 中村貴義; 芥川智行

    日本化学会第99回春季年会  2019年3月 

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  • アニオン型ナフタレンジイミド誘導体の電子移動度とカチオン構造の相関

    川崎 渉; 星野哲久; 武田貴志; 松田 若菜; 関 修平; 芥川智行

    日本化学会第99回春季年会  2019年3月 

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  • Development of multiblock arene-perfluoroarene macrocycle

    SATO; Kohei; NABEYA; Kota; MURAOKA; Takahiro; HOSHINO; Norihisa; AKUTAGAWA; Tomoyuki; KINBARA; Kazushi

    日本化学会第99回春季年会  2019年3月 

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  • Crystal Structure; Dielectric and Magnetic properties of OxalateBridged MnCr Complex with Supramolecular Cation of (Anilinium Derivatives)(Benzo[18]crown-6)

    U; Jiabing; TAKAHASHI; Kiyonori; HOSHINO; Norihisa; SUZUKI; Yasutaka; HISAKI; Ichiro; KAWAMATA; Jun; AKUTAGAWA; Tomoyuki; NAKAMURA; Takayoshi

    日本化学会第99回春季年会  2019年3月 

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  • 多様な酸性分子に応答する塩基性ベンゾチアゾール誘導体の発光特性とその結晶構造変化

    高橋慧瑚; 中根由太; 武田貴志; 星野哲久; 坂井賢一; 芥川智行

    日本化学会第99回春季年会  2019年3月 

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  • Sorption of Channel-type Macrocyclic Molecular Crystals with Structural Flexibility

    YUAN; Guohao; TAKEDA; Takashi; HOSHINO; Norihisa; AKUTAGAWA; Tomoyuki

    日本化学会第99回春季年会  2019年3月 

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  • 一次元鎖型銅錯体結晶の選択的気体吸着による誘電異常と吸着熱

    高橋仁徳; 星野哲久; 野呂真一郎; 芥川智行; 中村貴義

    第54回熱測定討論会  2018年10月 

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  • ジアルキルテレフタルアミド誘導体の固相における強誘電性

    川名萌枝子; 武田貴志; 星野哲久; 芥川智行

    日本化学会「低次元系光機能材料研究会」第8回サマーセミナー:複雑系材料の精密評価技術、物質・材料研究機構  2018年9月 

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  • 塩基性ベンゾチアゾール誘導体の発光クロミズム

    高橋慧瑚; 中根由太; 武田貴志; 星野哲久; 坂井賢一; 芥川智行

    日本化学会「低次元系光機能材料研究会」第8回サマーセミナー:複雑系材料の精密評価技術、物質・材料研究機構  2018年9月 

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  • 磁性薄膜エッジを利用したNi78Fe22/Alq3/Ni78Fe22ナノ接合素子の電気磁気特性

    佐々木悠馬; ムシスカ ロビン; 三澤 貴浩; 森 澄人; 小峰 啓史; 星野 哲久; 芥川 智行; 藤岡 正弥; 西井 準治; 海住 英生

    第79回応用物理学会  2018年9月 

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  • Tunnel Magnetocapacitance in Single-layered Fe/MgF2 Granular Films

    Robin Msiska; Shusaku Honjo; Yuki Asai; Masashi Arita; Atsushi Tsurumaki-Fukuchi; Yasuo Takahashi; Norihisa Hoshino; Tomoyuki Akutagawa; Osamu Kitakami; Masaya Fujioka; Junji Nishii; Hideo Kaiju

    第79回応用物理学会  2018年9月 

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  • Solid state ferroelectricity of bowl-shaped trithiasumanene derivatives

    呉 筧筠; 武田貴志; 星野哲久; 甲山雅也; 古川俊介; 斎藤雅一; 芥川智行

    日本化学会化学系学協会東北大会  2018年9月 

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  • Fluorescent responses of pyridyl benzothiazole derivative to acid molecules

    高橋慧瑚; 中根由太; 武田貴志; 星野哲久; 坂井賢一; 芥川智行

    日本化学会化学系学協会東北大会  2018年9月 

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  • Ferroelectricity Properties of Dialkyltelephthalamide Derivatives

    川名萌枝子; 武田貴志; 星野哲久; 芥川智行

    日本化学会化学系学協会東北大会  2018年9月 

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  • Molecular Arrangements and Physical Properties of Ion-Pairing Dianionic Naphthalendiimide Derivatives

    川崎渉; 武田貴志; 星野哲久; 松田若菜; 関修平; 芥川智行

    日本化学会化学系学協会東北大会  2018年9月 

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  • ボウル状トリチアスマネン誘導体の強誘電性

    呉 筧筠; 武田 貴志; 星野 哲久; 甲山 雅也; 古川 俊輔; 斎藤 雅一; 芥川 智行

    第12回分子科学討論会2018  2018年9月 

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  • テトラ[3,4]チエニレンテトラカルボン酸の可逆的かつ選択的なエタノールの吸着挙動

    小澤 優喬; 武田 貴志; 星野 哲久; 芥川 智行

    第12回分子科学討論会2018  2018年9月 

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  • 一次元鎖型Cu錯体による混合ガスフローからの選択的CO2吸脱着と誘電応答

    高橋 仁徳; 星野 哲久; 野呂 真一郎; 芥川 智行; 中村 貴義

    第12回分子科学討論会2018  2018年9月 

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  • アルキルアミド置換ヘリセン誘導体の二次元水素結合ネットワークを介した強誘電性

    姉帯 勇人; 武田 貴志; 星野 哲久; 小林 東史; 斎藤 望; 重野 真徳; 山口 雅彦; 芥川 智行

    第12回分子科学討論会2018  2018年9月 

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  • ピリジル基を有するベンゾチアゾール誘導体の発光クロミズムとメカニズム

    高橋 慧瑚; 中根 由太; 武田 貴志; 星野 哲久; 坂井 賢一; 芥川 智行

    第12回分子科学討論会2018  2018年9月 

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  • ビス尿素大環状化合物の結晶構造変化とガス収着

    原 国豪; 武田 貴志; 星野 哲久; 芥川 智行

    第12回分子科学討論会2018  2018年9月 

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  • ジアニオン性ナフタレンジイミド誘導体の分子配列と電子移動特性

    川崎 渉; 武田 貴志; 星野 哲久; 松田 若菜; 関 修平; 芥川 智行

    第12回分子科学討論会2018  2018年9月 

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  • プロトン化したヘキサメチレンテトラミンからなるイオン結晶の構造

    森田 萩乃; 星野 哲久; 芥川 智行; 綱島 亮

    第12回分子科学討論会2018  2018年9月 

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  • ジアルキルテレフタルアミド誘導体の強誘電性

    川名 萌枝子; 武田 貴志; 星野 哲久; 芥川 智行

    第12回分子科学討論会2018  2018年9月 

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  • キラルアルキル鎖を導入したピレンテトラアミドの分子集合と光学特性・強誘電性

    武田貴志; 姉帯勇人; 星野哲久; 芥川智行

    第29回基礎有機化学討論会  2018年9月 

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  • 折れ曲がり構造を有するテトラ[3,4]チエニレンテトラカルボン酸が形成する水素結合ネットワークと選択的な溶媒吸着

    武田貴志; 小澤優喬; 星野哲久; 芥川 智行

    第29回基礎有機化学討論会  2018年9月 

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  • Study on Tunnel Magnetocapacitance in Fe/MgF2 Nanogranular Films

    Robin Msiska; Shusaku Honjo; Yuki Asai; Masashi Arita; Atsushi Tsurumaki-Fukuchi; Yasuo Takahashi; Norihisa Hoshino; Tomoyuki Akutagawa; Osamu Kitakami; Masaya Fujioka; Junji Nishii; Hideo Kaiju

    第4回 マテリアルズ・インフォマティクス基礎研究  2018年9月 

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  • 磁性薄膜エッジを利用した分子ナノ接合素子の作製と電気磁気特性

    佐々木 悠馬; ムシスカ ロビン; 三澤 貴浩; 森 澄人; 小峰 啓史; 星野 哲久; 芥川 智行; 藤岡 正弥; 西井 準治; 海住 英生

    第4回 マテリアルズ・インフォマティクス基礎研究  2018年9月 

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  • Sold State Ferroelectricity of Bowl-Shaped Alkoxy-Substututed Trithiasumanenes

    Jianyun Wu; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    Tohoku University's Chemistry Summer School 2018  2018年8月 

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  • Control in Packing Structures and Electron Transport Properties of Ion-Pairing n-Type Semiconductor

    Ayumi Kawasaki; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    Tohoku University's Chemistry Summer School 2018  2018年8月 

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  • Ferroelectricities of Alkylamide- and Alkylester-substituted Helicene Derivatives

    Hayato Anetai; Takashi Takeda; Norihisa Hoshino; Higashi Kobayashi; Nozomi Saito; Masanori Shigeno; Masahiko Yamaguchi; Tomoyuki Akutagawa

    Tohoku University's Chemistry Summer School 2018  2018年8月 

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  • Diverse Crystal Structures and Gas Sorption Properties of Bis-Urea Macrocycles

    Guohao Yuan; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    Tohoku University's Chemistry Summer School 2018  2018年8月 

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  • Fluorescent Chromism of 2-(2-Hydroxyphenyl) Benzothiazole Derivative bearing Acid Sensing Pyridyl Group

    Keigo Takahashi; Yuta Nakane; Takashi Takeda; Norihisa Hoshino; Ken-ichi Sakai; Tomoyuki Akutagawa

    Tohoku University's Chemistry Summer School 2018  2018年8月 

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  • Molecular Assembly Structures and Dielectric Properties of Dialkyl terephthalamide Derivatives

    Moeko Kawana; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    Tohoku University's Chemistry Summer School 2018  2018年8月 

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  • Ferroelectric Non planar Helicene Derivatives bearing Alkylamide-Chains

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    The 43rd International Conference on Coordination Chemistry (ICCC2018)  2018年7月 

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    The 43rd International Conference on Coordination Chemistry (ICCC2018)  2018年7月 

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    The 43rd International Conference on Coordination Chemistry (ICCC2018)  2018年7月 

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    The 43rd International Conference on Coordination Chemistry (ICCC2018)  2018年7月 

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    The International Conference on Science and Technology of Synthetic Metals 2018 (ICSM 2018)  2018年7月 

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    The International Conference on Science and Technology of Synthetic Metals 2018 (ICSM 2018)  2018年7月 

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    日本化学会 第98春季年会  2018年3月 

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    日本化学会 第98春季年会  2018年3月 

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    日本化学会 第98春季年会  2018年3月 

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    日本化学会 第98春季年会  2018年3月 

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    日本化学会 第98春季年会  2018年3月 

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  • Control in π-Stacking Structure Using Cation-Anion Pairs in Naphthalenediimide Derivative

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    China-Japan Joint Meeting Exploring a Frontier in Molecular Ferroelectric Materials  2017年11月 

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  • Ferroelectricity of Non-planar Helicene Derivative bearing Alkylamide Chains

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    π-Figuration Japanese-German Symposium  2017年11月 

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  • Control in Molecular Assemblies of Cation-Anion Pairs in Naphthalenediimide Derivative

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    π-Figuration Japanese-German Symposium  2017年11月 

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  • Tunable Optical and Ferroelectric Properties of Hydrogen-Bonding Pyrene Derivative with Chiral Alkylamide Chains

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    The 12th International Symposium on Crystalline Organic Metals; Superconductors and Magnets (ISCOM2017)  2017年9月 

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    The 12th International Symposium on Crystalline Organic Metals; Superconductors and Magnets (ISCOM2017)  2017年9月 

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    The 12th International Symposium on Crystalline Organic Metals; Superconductors and Magnets (ISCOM2017)  2017年9月 

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  • Hydrogen-Bonding Assemblies of Alkylamide-Substituted Amphiphilic Isophthalic Acid Derivative

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    The 12th International Symposium on Crystalline Organic Metals; Superconductors and Magnets (ISCOM2017)  2017年9月 

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    第66回高分子討論会  2017年9月 

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  • Molecular Assemblies of Cation-Anion Pairs of Phenylsulfonate-substituted Naphthalenediimide Derivative

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    化学系学協会東北大会2017  2017年9月 

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  • Controls in Circularly Polarized Luminescence (CPL) and Ferroelectricity of Chiral Supramolecular Pyrene Assemblies

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    化学系学協会東北大会2017  2017年9月 

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  • Hydrogen-Bonding Assemblies of Amphiphilic Alkylamide-Substituted Isophthalic Acid Derivative with different Alkyl Chain Lengths

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    化学系学協会東北大会2017  2017年9月 

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    化学系学協会東北大会2017  2017年9月 

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    第11回分子科学討論会  2017年9月 

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    第11回分子科学討論会  2017年9月 

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    第11回分子科学討論会  2017年9月 

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    第11回分子科学討論会  2017年9月 

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    第11回分子科学討論会  2017年9月 

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    第11回分子科学討論会  2017年9月 

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  • Hydrogen-Bonding Molecular Assemblies of Alkylamide-Substituted Isophthalic Acid Derivatives with Different Alkyl Chain Lengths

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    第11回分子科学討論会  2017年9月 

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    第11回分子科学討論会  2017年9月 

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    第11回分子科学討論会  2017年9月 

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    低次元系光機能材料研究会 第 6 回サマーセミナー 2017  2017年9月 

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    低次元系光機能材料研究会 第 6 回サマーセミナー 2017  2017年9月 

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    低次元系光機能材料研究会 第 6 回サマーセミナー 2017  2017年9月 

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  • スルホン酸基を導入した2-(2’-ヒドロキシフェニル)ベンゾチアゾール結晶における分子構造変化と発光クロミズム

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    低次元系光機能材料研究会 第 6 回サマーセミナー 2017  2017年9月 

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  • テトラ[3,4]チエニレンテトラカルボン酸の形成する多様なホスト-ゲスト結晶と溶媒吸脱着挙動

    小澤優喬; 武田貴志; 星野哲久; 芥川智行

    低次元系光機能材料研究会 第 6 回サマーセミナー 2017  2017年9月 

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  • アルキルアミド置換ピレン誘導体の超分子構造の制御による強誘電性および円偏光発光(CPL)の制御

    姉帯勇人; 武田貴志; 星野哲久; 芥川智行

    低次元系光機能材料研究会 第 6 回サマーセミナー 2017  2017年9月 

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  • Ni78Fe22/Alq3/Ni78Fe22接合素子における量子・古典状態間遷移領域に関する研究

    佐々木悠馬; 三澤貴浩; 森澄人; 小峰啓史; 星野哲久; 芥川智行; 藤岡正弥; 西井準治; 海住英生

    第78回応用物理学会  2017年9月 

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  • Ni78Fe22/Alq3/Ni78Fe22ナノ接合素子の電気伝導特性

    三澤貴浩; 森澄人; 佐々木悠馬; 小峰啓史; 星野哲久; 芥川智行; 藤岡正弥; 西井準治; 海住英生

    第78回応用物理学会  2017年9月 

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  • 巨大負磁気抵抗効果を示す軸配位型鉄(III)ポルフィリン伝導体

    西美樹; 石井龍太; 花咲徳亮; 星野哲久; 芥川智行; 松田真生

    第78回応用物理学会  2017年9月 

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  • Ferroelectric Non-planar Helicene Derivatives with Allylamide-Chains

    Hayato Anetai; Higashi Kobayash; Nozomi Saito; Masanori Shigeno; Takashi Takeda; Norihisa Hoshino; Masahiko Yamaguchi; Tomoyuki Akutagawa

    Tohoku Univeristy’s Chemistry Summer School 2017  2017年8月 

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  • Diverse crystal structures of tetra[3,4]thienylenetetracarboxylic acid and their solvent adsorption properties

    Masataka Ozawa; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    Tohoku Univeristy’s Chemistry Summer School 2017  2017年8月 

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  • Hydrogen-Bonding Molecule Assemblies of Amphiphilic Isophthalic Acid Derivative with -CONHCnH2n+1 Group

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    Tohoku Univeristy’s Chemistry Summer School 2017  2017年8月 

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  • Crystal Structures and Fluorescence Behaviors of 2-(2’-Hydroxyphenyl)benzothiazole Derivatives

    Yuta Nakane; Takashi Takeda; Norihisa Hoshino; Ken-ichi Sakai; Tomoyuki Akutagawa

    The 24th Congress of the International Union of Crystallography (IUCr 2017)  2017年8月 

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  • Dielectric Responses of Metal-layered Perovskite Crystals Including Chiral Ammonium

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    Tohoku Univeristy’s Chemistry Summer School 2017  2017年8月 

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  • Selective Molecular Sorption Property of 2,2’-Diamino-4,4’-bithiazole

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    Tohoku Univeristy’s Chemistry Summer School 2017  2017年8月 

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  • Crystal Structures and Phase Transition Behaviors of Pillar[n]arene Crystals

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    The 24th Congress of the International Union of Crystallography (IUCr 2017)  2017年8月 

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  • Structural Control and Physical Properties of Dianionic Naphthalenediimide Derivative

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    The 24th Congress of the International Union of Crystallography (IUCr 2017)  2017年8月 

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    Takahiro Kobayashi; Norihisa Hoshino; Takashi Takeda; Tomoyuki Akutagawa

    The 24th Congress of the International Union of Crystallography (IUCr 2017)  2017年8月 

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  • Phase Transition; Crystal Structure; and Dielectric Response of Two-Dimensional Perovskites Including Chiral Ammonium

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    The 6th Asian Conference on Coordination Chemistry (ACCC6)  2017年7月 

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  • Ring-Type Molecular Assembly of Alkylamide-Substituted Isophthalic Acid

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    The 6th Asian Conference on Coordination Chemistry (ACCC6)  2017年7月 

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  • Circularly Polarized Luminescence (CPL); Fluorescence; and Ferroelectricity of Chiral Alkylamides-Substituted Pyrene Supramolecular-Assemblies

    Hayato Anetai; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    13th International Conference on Materials Chemistry (MC13)  2017年7月 

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  • Correlation between π-conduction electron and d-localised spin in axiallyligated iron tetrabenzoporphyrin conductors

    Miki Nishi; Norihisa Hoshino; Tomoyuki Akutagawa; Ryuta Ishii; Noriaki Hanasaki; Masaki Matsuda

    13th International Conference on Materials Chemistry (MC13)  2017年7月 

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  • Bithiazole-based Molecular Sorption Materials

    Hirohshi Nishiyama; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    13th International Symposium on Functional π-Electron Systems  2017年6月 

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  • Preparation and physical properties of tetra[3,4]thienylenetetracarboxylic acid and its alkylated derivatives

    Masataka Ozawa; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    13th International Symposium on Functional π-Electron Systems  2017年6月 

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  • テトラ[3,4]チエニレンテトラカルボン酸および誘導体の合成と物性

    小澤優喬; 武田貴志; 星野哲久; 芥川智行

    日本化学会第97回春季年会  2017年3月 

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  • マルチブロック型大環状化合物の熱結晶多形転移現象

    鍋谷光太; 村岡貴博; 星野哲久; 芥川智行; 梶谷 孝; 福島孝典; 金原数

    日本化学会第97回春季年会  2017年3月 

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  • スルホネート基を導入した2-(2’-ヒドロキシフェニル)ベンゾ チアゾール誘導体の分子構造と発光特性

    中根由太; 武田貴志; 星野哲久; 坂井賢一; 芥川智行

    日本化学会第97回春季年会  2017年3月 

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  • Control in Ferroelectricity and Optical Properties of Supramolecular Structures of Alkylamide-substituted Pyrene Derivatives

    ANETAI; Hayato; TAKEDA; Takashi; HOSHINO; Norihisa; AKUTAGAWA; Tomoyuki

    日本化学会第97回春季年会  2017年3月 

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  • 局在スピンを有する分子性導電体 TPP[FeIII(tbp)L2]2 (L = Br; Cl)の開発

    西 美樹; 石井龍太; 池田光雄; 花咲徳亮; 星野哲久; 芥川智行; 松田真生

    日本化学会第97回春季年会  2017年3月 

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  • Hydrogen-Bonding Molecular Assemblies of Alkylamide-Substituted Amphiphilic Isophthalic Acid Derivative

    LU; Chao; TAKEDA; Takashi; HOSHINO; Norihisa; AKUTAGAWA; Tomoyuki

    日本化学会第97回春季年会  2017年3月 

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  • キラルアンモニウムを導入した二次元ペロブスカイト結晶の相転移挙動,結晶構造および誘電応答

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    日本化学会第97回春季年会  2017年3月 

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  • グアニジニウム-スルホン酸塩の相転移,結晶構造および誘電応答

    小林貴博; 星野哲久; 武田貴志; 芥川智行

    日本化学会第97回春季年会  2017年3月 

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  • フェニルスルホネート置換ナフタレンジイミド誘導体が形成する分子集合体構造の制御と物性開拓

    川崎 渉; 武田貴志; 星野哲久; 芥川智行

    日本化学会第97回春季年会  2017年3月 

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  • ビチアゾール骨格を用いた分子性吸脱着材料の開発

    西山浩史; 武田貴志; 星野哲久; 芥川智行

    日本化学会第97回春季年会  2017年3月 

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  • ジアルコキシピラジノキノキサリンジオンの合成と物性

    武田貴志; 池元智拾; 星野哲久; 芥川智行

    日本化学会第97回春季年会  2017年3月 

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  • Fluorescent Dual Ion-Sensing of Crown-Ether Fused Quinoxalinone Derivative

    Yuta Nakane; Takashi Takeda; Norihisa Hoshino; Ken-ichi Sakai; Tomoyuki Akutagawa

    第12回日中有機半導体会議  2016年10月 

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  • Hydrogen-bonding Molecular Ferroelectrics and Ferroelastics

    Hayato Anetai; Shota Uchikawa; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    第12回日中有機半導体会議  2016年10月 

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  • Ferroelectricity and Electric Conductivity in Fluorescent Alkylamide-Substituted Pyrene Derivative

    Hayato Anetai; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    第12回日中有機半導体会議  2016年10月 

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  • x 型リチウムフタロシアニン結晶が有する空孔へのガス吸着特性と電気特性への影響

    西 美樹; 星野 哲久; 野呂 真一郎; 芥川 智行; 松田 真生

    第25回有機結晶シンポジウム  2016年9月 

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  • 薄膜エッジを利用したNi78Fe22/Alq3/Ni78Fe22 ナノ接合の作製とその構造・電気伝導特性

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    第77回応用物理学会春季学術講演会  2016年9月 

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  • アルキルアミド鎖を導入した三回対称性分子が形成する分子集合体構造と誘電物性

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    第10回分子科学討論会  2016年9月 

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  • 結晶内に空孔を有するx-LiPcの誘電特性とガス吸脱着特性、第10回分子科学討論会

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    第10回分子科学討論会  2016年9月 

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  • エラグ酸溶液への光照射によるクロミズムの発現とその反応メカニズム

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    第10回分子科学討論会  2016年9月 

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  • クラウンエーテル縮合型キノキサリノン誘導体によるカチオン−アニオン蛍光多重センシング

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    第10回分子科学討論会  2016年9月 

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  • キラルなアルキルアミド基を導入したピレンの分子集合構造と誘電物性

    姉帯 勇人; 武田 貴志; 星野 哲久; 芥川 智行

    第10回分子科学討論会  2016年9月 

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  • 分子性結晶におけるプロトン移動と強弾性機能の発現

    内川 翔太; 安田 陽; 星野 哲久; 武田 貴志; 芥川 智行

    第10回分子科学討論会  2016年9月 

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  • Multiple Cation-Anion Sensing of Crown-Ether Fused Quinoxalinone Derivative

    Yuta Nakane; Takashi Takeda; Norihisa Hoshino; Ken-ichi Sakai; Tomoyuki Akutagawa

    The 15th International Conference on Molecule-Based Magnets ICMM2016  2016年9月 

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  • Dielectric Response of Molecular Rotator in Hydrogen-Bonding Copper Coordination Complexes

    Kiyonori Takahashi; Norihisa Hoshino; Tomoyuki Akutagawa

    The 15th International Conference on Molecule-Based Magnets ICMM2016  2016年9月 

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  • Dielectric Relaxation of Glassy Assembly of Alkylamide-Substituted Pararosaniline Derivative

    Satoru Akahane; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akuragawa

    Rising Star Pre-conference of ICMM 2016; Workshop for Young Investigators on Functional Molecular Materials and Molecular Related Magnetism  2016年9月 

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  • 曲面π共役分子スマネン誘導体が示す結晶中での特異な配向特性

    燒山佑美; Ngamsomprasert Niti; 春木理恵; 足立伸一; 熊井玲児; 山下智史; 中澤康浩; 星野哲久; 芥川智行; 櫻井英博

    第27回基礎有機化学討論会  2016年9月 

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  • Phase Transition Behavior and Molecular Motion of Alkylamide-Substituted Triphenylmethanol Derivative

    S. Akahane; T. Takeda; N. Hoshino; T. Akutagawa

    Tohoku Univeristy’s Chemistry Summer School 2016  2016年8月 

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  • Chromism of Ellagic Acid Solution by Photo Irradiation

    H. Tokutomi; T. Takeda; N. Hoshino; T. Akutagawa

    Tohoku Univeristy’s Chemistry Summer School 2016  2016年8月 

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  • Ferroelectricity and Optical Properties of Pyrene Derivative with Alkylamide Group

    H. Anetai; T. Takeda; N. Hoshino; T. Akutagawa

    Tohoku Univeristy’s Chemistry Summer School 2016  2016年8月 

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  • Hydrogen-Bonding Networks and Ferroelasticity in Molecular Crystals

    S. Uchikawa; A. Yasuda; N. Hoshino; T. Takeda; T. Akutagawa

    Tohoku Univeristy’s Chemistry Summer School 2016  2016年8月 

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  • Design of Proton Ratchet in Hydrogen-Bonding H2PO4- based Proton Conductor

    M. Takahashi; N. Hoshino; T. Takeda; T. Kikuchi; T. Akutagawa

    Tohoku Univeristy’s Chemistry Summer School 2016  2016年8月 

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  • Multiple Ion Sensing Quinoxalinone Derivatives

    Y. Nakane; T. Takeda; N. Hoshino; K. Sakai; T. Akutagawa

    International Conference on Coordination Chemistry (ICCCC) 2016  2016年7月 

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  • Fluorescence and Ferroelectric Properties of Pyrene Derivative bearing Alkylamide Group

    H. Anetai; T. Takeda; N. Hoshino; T. Akutagawa

    International Conference on Coordination Chemistry (ICCCC) 2016  2016年7月 

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  • Hydrogen-Bonding Molecular Assemblies of Alkylamide-Substituted Benzene Carboxylic Acid Derivative

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    International Conference on Science and Technology of Synthetic Metals 2016 (ICSM 2016)  2016年6月 

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  • Phase Transition and Dielectric Response of Alkylamide-Subtitled Pararosaniline Derivative

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    International Conference on Science and Technology of Synthetic Metals 2016 (ICSM 2016)  2016年6月 

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  • Fluorescent Multiple Ion-Sensing of Crown-Ether Fused Quinoxalinone Derivative

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    International Conference on Science and Technology of Synthetic Metals 2016 (ICSM 2016)  2016年6月 

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  • Chromism of Ellagic Acid Solution by Photo Irradiation

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    International Conference on Science and Technology of Synthetic Metals 2016 (ICSM 2016)  2016年6月 

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  • Ferroelastic Domain Switching in Boric Acid Single Crystal

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    International Conference on Science and Technology of Synthetic Metals 2016 (ICSM 2016)  2016年6月 

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  • Molecular Aggregation and Fluorescence of Pyrene Derivative bearing Chiral Alkylamide

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    International Conference on Science and Technology of Synthetic Metals 2016 (ICSM 2016)  2016年6月 

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    日本化学会第96春季年会 (2016)  2016年3月 

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  • アルキルアミド基を有するパラローズアニリン誘導体の相転移挙動と誘電応答

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  • キラルな分岐アルキルアミド基を有するピレン誘導体の分子会合挙動と発光特性

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  • クラウンエーテル縮合型キノキサリノン誘導体における蛍光多重イオンセンシング

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    日本化学会第96春季年会 (2016)  2016年3月 

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  • プロトン受容性基を有する複素環式アミンを対カチオンとした混合原子価金属酸化物クラスター[PMoVnMoVI12-nO40](3+n)-の構造と交流電場応答

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  • アルキルアミド基を有するピレン誘導体の発光特性および強誘電性

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  • 水素結合鎖を持つ擬一次元Cu錯体の配位子間相互作用の制御と相転移挙動

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    錯体化学会第65回討論会  2015年9月 

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  • 強誘電性アルキルアミド置換ピレン誘導体におけるアルキル鎖の影響

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  • キノキサリノン誘導体のラクタム−ラクチム互変異性によるアニオン−カチオン二重センシング

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  • n-アルキルアンモニウムリン酸塩の強弾性相転移メカニズムと力学特性

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  • 強弾性体ホウ酸結晶の水素結合様式と機械的刺激に対する応答

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  • リチウムフタロシアニンラジカルの誘電特性&#183;ガス吸着特性

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  • 強誘電性ディスコチックヘキサゴナルカラムナー相へのイオンチャネル構造の導入

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    第9回分子科学討論会  2015年9月 

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  • (Halo-anilinium)(H2PO4)塩における水素結合構造の次元性およびプロトン伝導挙動の相関

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    第9回分子科学討論会  2015年9月 

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  • Ferroelectricity in Fluorescent Alkylamide-Substituted Pyrene Derivative

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    11th International Symposium on Crystalline Organic Metals; Superconductors and Magnets (ISCOM 2015)  2015年9月 

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  • Ferroelectricity; Electric Conductivity; and Fluorescence of Alkylamide-Substituted Pyrene Derivative

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    Campus Asia Tohoku University Summer School  2015年8月 

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  • Ferroelasticity of Two-Dimensional Hydrogen-Bonding Boric Acid Crystal

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    Campus Asia Tohoku University Summer School  2015年8月 

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  • Ferroelastcic Phase Transition Mechanism of n-Alkylammonium Dihydrogen Phosphate

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    Campus Asia Tohoku University Summer School  2015年8月 

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  • Relationship between Structural Flexibilities and Gas Adsorption Properties of One-Dimensional Copper(II) Polymers with Paddle-Wheel Units

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    Campus Asia Tohoku University Summer School  2015年8月 

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  • ation-Anion Dual Sensing of Fluorescent Quinoxalinone Derivative

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    The 5th Asian Conference on Coordination Chemistry (ACCC5)  2015年7月 

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  • Relationship between Gas Adsorption and Structural Flexibility of [Cu(II)2(p-XBenzoate)4(pyrazine)]n (X = Br; or I) Polymers by Hirshfeld Surface Analyses

    Kiyonori Takahashi; Norihisa Hoshino; Shin-ichiro Noro; Takayoshi Nakamura; Tomoyuki Akutagawa

    The 5th Asian Conference on Coordination Chemistry (ACCC5)  2015年7月 

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  • Crystal-to-Crystal Structural Transformation of (Imidazolium)(3-Hydroxy-2-quinoxalinecarboxylate) through H2O Adsorption&#8211;Desorption

    Yuya Yoshiia; Ken-ichi Sakaib; Norihisa Hoshino; Takashi Takeda; Shin-ichiro Noro; Takayoshi Nakamura; Tomoyuki Akutagawa

    The 5th Asian Conference on Coordination Chemistry (ACCC5)  2015年7月 

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  • Cation and Anion Sensing by Simple Quinoxalinone Derivative

    Yuta Nakane; Takashi Takeda; Norihisa Hoshino; Ken-ichi Sakai; Tomoyuki Akutagawa

    16th International Symposium on Novel Aromatic Compounds  2015年7月 

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  • Commensurate-Incommensurate Phase Transitions and Physical Properties of Layered Complexes of (CnH2n+1NH3)2CuCl4 国際会議

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    4th German-Japanese University President’s Conference Workgroup meeting No.2  2015年5月 

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  • 新規p-d系鉄(III)テトラベンゾポルフィリンを用いた分子性導電体の開発

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    日本化学会第95回春年会  2015年3月 

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  • (Imidazolium)(3-Hydroxy-2-quinoxalinecarboxylate)結晶の水吸脱 着に伴う構造相転移

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    日本化学会第95回春年会  2015年3月 

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  • キノキサリノン誘導体のカチオン-アニオン認識

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  • Hirshfeld 表面解析を用いた一次元鎖状 Paddle-wheel 型 Cu(II)錯 体のガス吸着特性と分子間相互作用の評価

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    日本化学会第95回春年会  2015年3月 

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  • 強誘電性アルキルアミド置換ピレン誘導体へのキラル構造の導入

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    日本化学会第95回春年会  2015年3月 

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  • テトラアルキルアミド置換ジベンゾ[18]crown-6誘導体の合成と機能開拓

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    日本化学会第95回春年会  2015年3月 

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    第4回CSJ化学フェスタ  2014年10月 

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    第4回CSJ化学フェスタ  2014年10月 

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  • キノキサリノン誘導体によるカチオン‐アニオンセンシング

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    第4回CSJ化学フェスタ  2014年10月 

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  • ハロゲン置換メシチレン誘導体の動的物性に及ぼす置換基効果

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    第8回分子科学討論会2014  2014年9月 

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  • テトラアミノ-p -ベンゾキノンの結晶構造と溶液中における二量化反応

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    第8回分子科学討論会2014  2014年9月 

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  • ジシアノ鉄(III)テトラベンゾポルフィリンからなる分子性導電体の作製

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    第8回分子科学討論会2014  2014年9月 

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  • 混合原子価[PMoVnMoVI12-nO40](3+n)-クラスターの誘電特性

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    第8回分子科学討論会2014  2014年9月 

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  • アルキルアンモニウム−ピリジンおよびベンゼンスルホン酸塩の結晶構造と相転移挙動

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    第8回分子科学討論会2014  2014年9月 

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  • アミノピリジニウム/キラルクラウンエーテル誘導体カチオンを導入した[Ni(dmit)2]-錯体結晶の合成と物性

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    第8回分子科学討論会2014  2014年9月 

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  • アニリニウム誘導体とリン酸アニオンから成る水素結合性分子結晶の構造とプロトン伝導挙動

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  • アルキルアミド置換ピレン誘導体の光学特性と強誘電性

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    第8回分子科学討論会2014  2014年9月 

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  • アルキルアミド置換ジベンゾ[18]crown-6誘導体の合成と機能開拓

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    第8回分子科学討論会2014  2014年9月 

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  • クラウンエーテル縮環型キノキサリノン誘導体の合成とカチオン−アニオン二重センシング特性

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    第8回分子科学討論会2014  2014年9月 

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  • 三角白金格子を持つV&egrave;zes’ Red Salt を用いた有機−無機ハイブリッド集合体の作製

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    第8回分子科学討論会2014  2014年9月 

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  • Ru二核錯体とTCNQ誘導体からなる電荷移動型集積体の不活性種ドーピングによる電子物性制御

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    第8回分子科学討論会2014  2014年9月 

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  • 嵩高い置換基を導入した一次元鎖Cu(II) 錯体の分子間相互作用と物性の相関

    高橋仁徳; 星野哲久; 野呂真一郎; 中村貴義; 芥川智行

    錯体化学第64回討論会  2014年9月 

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  • 相補的な2つの水素結合によって連結されたReIII/IV混合原子価錯体の構造と性質

    古舘保; 横井遼太郎; 藤才浩; 磯田恭佑; 星野哲久; 芥川智行; 田所誠

    錯体化学第64回討論会  2014年9月 

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  • クラウンエーテル縮環型キノキサリノン誘導体の合成およびカチオンとアニオン認識に対する光学応答

    中根由太; 武田貴志; 星野哲久; 坂井賢一; 芥川智行

    第25回基礎有機化学討論会  2014年9月 

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  • [Li@C60](PF6)の反強誘電的相転移

    青柳忍; 杉本邦久; 岡田洋史; 星野哲久; 芥川智行

    日本物理学会2014秋季大会  2014年9月 

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  • アレーンオリゴアミドが示す自己集積挙動と強誘電体物性

    武田貴志; 姉帯勇人; 宍戸勇太; 星野哲久; 芥川智行

    第25回基礎有機化学討論会  2014年9月 

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  • アルキルアミド置換ピレン誘導体の誘電物性と自己集積化挙動

    姉帯勇人; 武田貴志; 星野哲久; 芥川智行

    第25回基礎有機化学討論会  2014年9月 

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  • リン酸塩から成る水素結合性分子結晶の固相プロトン伝導に関する検討

    吉井祐弥; 武田貴志; 星野哲久; 芥川智行

    日本化学会「低次元系光機能材料研究会」第3回サマーセミナー 有機−無機複合材料の光化学と新展開  2014年9月 

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  • n-ドデシルアンモニウム/3-ピリジンスルホン酸およびベンゼンスルホン酸塩の結晶構造と相転移挙動

    舟田敦司; 星野哲久; 武田貴志; 芥川智行

    日本化学会「低次元系光機能材料研究会」第3回サマーセミナー 有機−無機複合材料の光化学と新展開  2014年9月 

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  • 極性置換基を導入したPaddle-wheel型銅二核錯体の固気反応による構造と色の変化

    高橋仁徳; 星野哲久; 野呂真一郎; 中村貴義; 芥川智行

    日本化学会「低次元系光機能材料研究会」第3回サマーセミナー 有機−無機複合材料の光化学と新展開  2014年9月 

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  • Synthesis of Crown-Ether Fused Quinoxalinone Derivative and its Optical Responses for Cation &#8211; Anion Sensing

    Yuta Nakane; Takashi Takeda; Norihisa Hoshino; Ken-ichi Sakai; Tomoyuki Akutagawa

    Tohoku University’s Shmeistry Summer School 2014  2014年8月 

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  • Moelcular Aggregation and Ferroelectric Properties of Alkylamide-Substituted Pyrene Derivative

    Hayato Anetai; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    Tohoku University’s Shmeistry Summer School 2014  2014年8月 

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  • Crystal Structures and Physical Properties of n &#8211; Dodecylammonium / 3-Pyridine Sulfonate and Benzene Sulfonate

    Atsushi Funada; Norihisa Hoshino; Takashi Takeda; Tomoyuki Akutagawa

    Tohoku University’s Shmeistry Summer School 2014  2014年8月 

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  • Crystal Structures and Gas Adsorption-Desorption Properties of Paddle-Wheel Type Copper(II) Complexes with Bulky Benzoate Ligands

    Kiyonori Takahashi; Norihisa Hoshino; Shin-ichiro Noro; Takayoshi Nakamura; Tomoyuki Akutagawa

    Tohoku University’s Shmeistry Summer School 2014  2014年8月 

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  • Rotational Dynamics and Dielectric Properties of in-plane Molecular Rotators

    Jun-ichi Ichikawa; Norihisa Hoshino; Takashi Takeda; Tomoyuki Akutagawa

    Tohoku University’s Shmeistry Summer School 2014  2014年8月 

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  • Crystal and Electronic Structures of Tetraamino- and Tetrakis(dimethylamino)-p-benzoquinones

    Masahiro Sato; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    Tohoku University’s Shmeistry Summer School 2014  2014年8月 

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  • Antiferroelectric Ordering of Lithium Cation Encapsulated in C60 Fullerene

    Shinobu Aoyagi; Kunihisa Sugimoto; Hiroshi Okada; Norihisa Hoshino; Tomoyuki Akutagawa

    The 10th Japan-Korea Conference on Ferroelectrics  2014年8月 

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  • Dielectric Phase Transition of [Li@C60](PF6) at Low Temperature

    Shinobu Aoyagi; Kunihisa Sugimoto; Hiroshi Okada; Norihisa Hoshino; Tomoyuki Akutagawa

    The 23rd International Union of Crystallography (IUCr) Congress  2014年8月 

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  • オルガノゲル材料を用いたナノ構造と新機能探索

    吉井祐弥; 宍戸勇太; 武田貴志; 星野哲久; 芥川智行

    材料フェスタ in 仙台  2014年7月 

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  • Color and Structural Changes of One-Dimensional Cu(II) Complexes Induced by Vapor Chemisorptions

    Kiyonori Takahashi; Norihisa Hoshino; Shin-ichiro Noro; Takayoshi Nakamura; Tomoyuki Akutagawa

    the18th International Symposium on Advanced Display Materials and Devices (ADMD 2014)  2014年7月 

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  • Optical Responses of Crown-Ether Fused Quinoxalinone Derivative for Cation &#8211; Anion Sensing

    Yuta Nakane; Takashi Takeda; Norihisa Hoshino; Ken-ichi Sakai; Tomoyuki Akutagawa

    the18th International Symposium on Advanced Display Materials and Devices (ADMD 2014)  2014年7月 

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  • Liquid Crystalline Properties; Ferroelectricity; and Fluorescence of Alkylamide-Substituted Pyrene Derivative

    Hayato Anetai; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    the18th International Symposium on Advanced Display Materials and Devices (ADMD 2014)  2014年7月 

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  • Intrinsic Proton Conductor of o-Haloanilinium Derivative and Phosphate Anion

    Yuya Yoshii; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagwa

    the18th International Symposium on Advanced Display Materials and Devices (ADMD 2014)  2014年7月 

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  • Phase Transition Behavior and Physical Properties of Ferroelastic n-Alkylammonium Dihydrogen Phosphate

    Akira Yasuda; Norihisa Hoshino; Takashi Takeda; Tomoyuki Akutagawa

    the18th International Symposium on Advanced Display Materials and Devices (ADMD 2014)  2014年7月 

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  • VAPOR CHEMISORPTIONS; STRUCTURAL CHANGES; AND MAGNETIC PROPERTIES OF COPPER(II) COMPLEX

    Kiyonori Takahashi; Norihisa Hoshino; Shin-ichiro Noro; Takayoshi Nakamura; Tomoyuki Akutagawa

    The 14th International Conference on Molecule-Based Magnets (ICMM2014)  2014年7月 

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  • Synthesis; Fluorescence and Polarization Properties of Alkylamide Substituted Pyrene Derivatives

    Hayato Anetai; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    International Conference on Science and Technology of Synthetic Metals 2014 (ICSM 2014)  2014年6月 

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  • Preparations; Crystal Structures; and Physical Properties of Binuclear Cu(II) Complexes bearing Bulky Ligands

    Kiyonori Takahashi; Norihisa Hoshino; Shin-ichiro Noro; Takayoshi Nakamura; Tomoyuki Akutagawa

    International Conference on Science and Technology of Synthetic Metals 2014 (ICSM 2014)  2014年6月 

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  • Phase Transition Mechanism of Ferroelastic n-Alkylammonium Dihydrogen Phosphate

    Akira Yasuda; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    International Conference on Science and Technology of Synthetic Metals 2014 (ICSM 2014)  2014年6月 

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  • Intrinsic Proton Conductor of Hydrogen-Bonding Molecular Crystals of o-Fluoroanilinium-Phosphate

    Yuya Yoshii; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    International Conference on Science and Technology of Synthetic Metals 2014 (ICSM 2014)  2014年6月 

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  • Ferroelectricity and Nanofiber Network of Alkylamide-substituted Benzene Derivatives

    Tomoyuki Akutagawa; Hayato Anetai; Yuta Shishido; Takashi Takeda; Norihisa Hoshino

    International Conference on Science and Technology of Synthetic Metals 2014 (ICSM 2014)  2014年6月 

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  • TAKAHASHI Kiyonori; HOSHINO Norihisa; NORO Shin-ichiro; NAKAMURA Takayoshi; AKUTAGAWA Tomoyuki

    Controls in Interchain-Interaction; Physical Properties of Binuclear Copper(II) Polymers with Bulky Benzoate Ligands

    日本化学会第94春季年会(2014)  2014年3月 

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  • n-ドデシルアンモニウム-ピリジンスルホン酸塩の結晶構造と動的物性

    舟田敦司; 星野哲久; 武田貴志; 芥川智行

    日本化学会第94春季年会(2014)  2014年3月 

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  • Phase Transition Behaviors of Ferroelastic n-Alkylammonium Dihydrogen Phosphate

    Akira Yasuda; Norihisa Hoshino; Takashi Takeda; Tomoyuki Akutagawa

    International Senior Project Conference in Engineering and Technology  2014年3月 

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  • アルキルアミド置換ピレン誘導体の合成と物性

    姉帯勇人; 武田貴志; 星野哲久; 芥川智行

    日本化学会第94春季年会(2014)  2014年3月 

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  • trans-anti-trans-dicyclohexano[18]crown-6/4-aminopyridinium超分子カチオンを導入した[Ni(dmit)2]結晶の構造と誘電性

    渡辺 大樹; 久保 和也; 星野 哲久; 芥川 智行; 野呂 真一郎; 中村 貴義

    日本化学会第94春季年会(2014)  2014年3月 

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  • ハロゲン置換ベンゼン誘導体の対称性と動的物性の相関

    市川順一; 星野哲久; 武田貴志; 芥川智行

    日本化学会第94春季年会(2014)  2014年3月 

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  • トリアゾール縮環型p-ベンゾキノン誘導体の結晶構造と電荷移動錯体中の選択的二量化反応

    佐藤匡裕; 武田貴志; 星野哲久; 芥川智行

    日本化学会第94春季年会(2014)  2014年3月 

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  • リン酸塩から成る水素結合性分子結晶のプロトン伝導挙動

    吉井祐弥; 武田貴志; 星野哲久; 芥川智行

    日本化学会第94春季年会(2014)  2014年3月 

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  • マルチブロック両親媒分子から成る有機結晶の相転移現象

    嶋 建也; 村岡貴博; 星野哲久; 芥川智行; 金原 数

    日本化学会第94春季年会(2014)  2014年3月 

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  • 複数の水素結合部位を有する超分子カチオン結晶の構造と物性

    山田 晃弘; 久保 和也; 星野 哲久; 芥川 智行; 野呂 真一郎; 中村 貴義

    日本化学会第94春季年会(2014)  2014年3月 

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  • 蛍光性キノキサリノン誘導体の合成とカチオン‐アニオンセンシング

    中根由太; 武田貴志; 星野哲久; 坂井賢一; 芥川智行

    日本化学会第94春季年会(2014)  2014年3月 

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  • 強弾性体n-アルキルアンモニウム リン酸塩の相転移挙動と物性

    安田 陽; 星野哲久; 武田貴志; 芥川智行

    日本化学会第94春季年会(2014)  2014年3月 

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  • 三角白金格子を持つVerzes’Red Saltsの構造と物性

    藤田成樹; 星野哲久; 武田貴志; 芥川智行

    日本化学会第94春季年会(2014)  2014年3月 

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  • 混合原子価ポリオキソメタレート[MoV2MoVI16O54(SO3)2]6-クラスターの誘電特性

    中村一平; 星野哲久; 芥川智行; 綱島亮

    日本化学会第94春季年会(2014)  2014年3月 

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  • アルキルアンモニウム-スルホン酸塩の結晶構造と相転移挙動

    舟田敦司; 星野哲久; 武田貴志; 芥川智行

    高分子ハイブリッド材料研究センター(PHyM)若手シンポジウム2013  2013年12月 

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  • Pt(II)三核錯体の結晶構造と物性

    藤田成樹; 星野哲久; 武田貴志; 芥川智行

    高分子ハイブリッド材料研究センター(PHyM)若手シンポジウム2013  2013年12月 

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  • テトラアミノ-p-ベンゾキノン誘導体の結晶構造と電子状態

    佐藤匡裕; 武田貴志; 星野哲久; 芥川智行

    高分子ハイブリッド材料研究センター(PHyM)若手シンポジウム2013  2013年12月 

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  • 6置換ベンゼン誘導体を用いたin-plane分子ローターの動的挙動と誘電物性

    市川順一; 星野哲久; 武田貴志; 芥川智行

    多元研発表会2013  2013年12月 

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  • 蛍光性キノキサリノン誘導体の合成とカチオン-アニオンセンシング

    中根由太; 武田貴志; 星野哲久; 坂井賢一

    多元研発表会2013  2013年12月 

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  • Structural Changes of One-dimensional Copper(II) Complexes though H2O and Pyridine Chemisorptions

    Kiyonori Takahashi; Norihisa Hoshino; Shin-ichiro Noro; Takayoshi Nakamura; Tomoyuki Akutagawa

    4th Asian Conference on Coordination Chemsitry  2013年11月 

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  • Phase Transitions and Dielectric Properties of Organic-Inorganic Layered Complexes of (CnH2n+1NH3)2CuCl4

    Norihisa Hoshino; Shunsaku Tamura; Tomoyuki Akutagawa

    4th Asian Conference on Coordination Chemsitry  2013年11月 

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  • Paddle-Wheel型銅(II)一次元錯体結晶の溶媒蒸気との反応による構造・物性変化

    高橋仁徳; 星野哲久; 芥川智行

    錯体化学会第63回討論会  2013年11月 

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  • Crystal Structures and Correlations Between the Electron-Transfer and Ion-Recognition in Quinone- and Hydroquinone-Fused [18]crown-6

    Takayuki Kobayashi; Takashi Takeda; Norihisa Hoshino; Tomoyuki Akutagawa

    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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  • Structural Phase Transition and Dielectric Properties of Dibromoiodomesitylene

    Jun-ichi Ichikawa; Norihisa Hoshino; Takashi Takeda; Tomoyuki Akutagawa

    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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  • Structural Changes and Physical Properties of Copper(II) Complex by Pyridine Chemsorption

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    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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    International Symposium for the 70th Anniversary of the Tohoku Branch of teh Chemical Society of Japan  2013年9月 

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    Tohoku University Campus Asia Summer School 2013  2013年8月 

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    Tohoku University Campus Asia Summer School 2013  2013年8月 

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    The 5th International Symposium on nano and Supramoelcular chemistry  2013年8月 

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    The 5th International Symposium on nano and Supramoelcular chemistry  2013年8月 

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    The 15th Asian Chemical Congress (ACC15)  2013年8月 

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    The 10th International Symposium on Crystalline Organic Metals; Superconductors adn Magnets (ISCOM2013)  2013年7月 

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    The 10th International Symposium on Crystalline Organic Metals; Superconductors adn Magnets (ISCOM2013)  2013年7月 

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    11th International Symmposium on Functional &#61552;-Electrion Systems  2013年6月 

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    日本化学会第93春季年会(2013)  2013年3月 

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    日本化学会第93春季年会(2013)  2013年3月 

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    日本化学会第93春季年会(2013)  2013年3月 

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    日本化学会第93春季年会(2013)  2013年3月 

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    日本化学会第93春季年会(2013)  2013年3月 

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    日本化学会第93春季年会(2013)  2013年3月 

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    日本化学会第93春季年会(2013)  2013年3月 

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    1st International Conference on Emerging Advanced Nanomaterials (ICEAN)  2012年10月 

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    1st International Conference on Emerging Advanced Nanomaterials (ICEAN)  2012年10月 

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    錯体化学会 第62回討論会  2012年9月 

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    第6回分子科学討論会2012  2012年9月 

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    第6回分子科学討論会2012  2012年9月 

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  • Multistep Structural Phase Transitions of Organic-Inorganic Hybrid (CnH2n+1NH3)2CuCl4

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    40 International Conference on Coordination Chemistry (ICCC40)  2012年9月 

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    40 International Conference on Coordination Chemistry (ICCC40)  2012年9月 

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    40 International Conference on Coordination Chemistry (ICCC40)  2012年9月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • Formation of organogels in Hydrogen-bonding (Aniliniums)-(L-Tartarate) Binary Compounds

    Yuuya Yoshii; Norihisa Hoshino; Tomoyuki Akutagawa

    KJF International Conference on Organic Materials for Electronics and Photonics 2012  2012年8月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • Structural and Thermal Properties of Organic-Inorganic Hybrid (CnH2n+1NH3)2CuCl4

    Shunsaku Tamura; Norihisa Hoshino; Tomoyuki Akutagawa

    KJF International Conference on Organic Materials for Electronics and Photonics 2012  2012年8月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • Crystal Structures and CO2 Adsorption-Desorption Properties of One-Dimensional Paddle-Wheel Type Cu(II) Coordination Polymers

    Kiyonori Takahashi; Norihisa Hoshino; Tomoyuki Akutagawa

    KJF International Conference on Organic Materials for Electronics and Photonics 2012  2012年8月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • CRYSTAL STRUCTURES AND REDOX PROPERTIES OF QUINO[18]CROWN-6 AND DIQUINO[18]CROWN-6

    T. Kobayashi; T. Takeda; N. Hoshino; T. Akutagawa

    International Conference on Science and Technology of Synthetic Metals 2012 (ICSM 2012)  2012年7月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • IELECTRIC RESPONSES; MOLECULAR MOTIONS; and GAS-ADSORPTION PROPERTIES OF PADDLE-WHEEL TYPE COODINATION POLYMERS

    T. Akutagawa; K. Takahashi; N. Hoshino; S. Noro; T. Nakamura

    International Conference on Science and Technology of Synthetic Metals 2012 (ICSM 2012)  2012年7月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • リン酸および酒石酸アニオンから成る分子結晶の構造と誘電物性

    吉井祐弥; 星野哲久; 菊地毅光; 芥川智行

    東北大学多元物質科学研究所 高分子・ハイブリッド材料研究センター 2012 PHyMシンポジウム  2012年6月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • 銅二核錯体から成る分子結晶の巨大誘電応答

    高橋仁徳; 星野哲久; 菊地毅光; 芥川智行

    東北大学多元物質科学研究所 高分子・ハイブリッド材料研究センター 2012 PHyMシンポジウム  2012年6月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • 有機−無機ハイブリッド型二次元シート状化合物(CnH2n+1NH3)2CuCl4の構造相転移

    田村駿作; 星野哲久; 芥川智行

    日本化学会第92春季年会  2012年3月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • (アニリニウム)-(L-酒石酸アニオン)から成る水素結合性分子集合体が形成する分子性結晶とオルガノゲル

    吉井祐弥; 星野哲久; 芥川智行

    日本化学会第92春季年会  2012年3月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • 極性配位子をもつPaddle-Wheel 型銅二核錯体一次元鎖ポリマーの合成と結晶構造

    高橋仁徳; 星野哲久; 芥川智行

    日本化学会第92春季年会  2012年3月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • ルマジンのプロトン状態制御による光・電子機能化

    坂井賢一; 長原健太; 星野哲久; 芥川智行

    日本化学会第92春季年会  2012年3月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • Dielectric Responses of Binuclear Cu(II)-Cu(II) Complexes Bearing Rotational Adamantyl Ligands

    Kiyonori Takahashi; Norihisa Hoshino; Takemitsu Kikuchi; Qiong Ye; Takayoshi Nakamura; Tomoyuki Akutagawa

    3rd Asian Conference on Coordination Chemistry (ACCC3)  2011年10月 

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    記述言語:英語   会議種別:口頭発表(一般)  

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  • リン酸および酒石酸アニオンから成る分子性結晶の結晶構造と誘電物性

    吉井 祐弥; 星野 哲久; 芥川 智行

    第5回分子科学討論会2011  2011年9月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • アダマンチル基を配位子としたPaddle-Wheel型銅二核錯体の巨大誘電応答

    高橋仁徳; 星野哲久; 菊地毅光; Qiong Ye; 中村貴義; 芥川智行

    第61回錯体化学討論会  2011年9月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • リン酸および酒石酸アニオンから成る分子結晶の構造と誘電物性

    吉井祐弥; 星野哲久; 菊地毅光; 芥川智行

    2011 PHyMシンポジウム  2011年6月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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  • 銅二核錯体から成る分子結晶の巨大誘電応答

    高橋仁徳; 星野哲久; 菊地毅光; 芥川智行

    2011 PHyMシンポジウム  2011年6月 

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    記述言語:日本語   会議種別:口頭発表(一般)  

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受賞

共同研究・競争的資金等の研究

  • 分子ローターの回転運動を利用した固体熱流制御材料の開発

    2020年11月 - 2021年11月

    住友財団  基礎科学研究助成 

    星野哲久

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    担当区分:研究代表者 

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  • 金属錯体結晶の次元性や相転移を利用した熱流束の制御

    研究課題/領域番号:20K05535  2020年4月 - 2023年3月

    日本学術振興会  科学研究費助成事業 基盤研究(C)  基盤研究(C)

    星野 哲久

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    配分額:4290000円 ( 直接経費:3300000円 、 間接経費:990000円 )

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  • 多核金属錯体によるスピントロニクス材料の開発

    2017年4月 - 2019年3月

    日本学術振興会  科学研究費 若手研究(B) 

    星野 哲久

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    担当区分:研究代表者  資金種別:競争的資金

    多核金属錯体をベースとした分子性スピントロニクス材料の開発を行う。分子内で三角形型にフラストレートした孤立dスピンと、ドナー性拡張π電子系有機配位子を併せ持つ多核金属錯体をベースとして、部分酸化塩や電荷移動錯体を合成することで、フラストレートしたd電子と導電カラムのπ電子が強く相互作用した導電性分子結晶を作成する。量子化dスピンの状態変化による電気伝導性のスイッチング(非線形・量子化・負性磁気抵抗など)や、伝導π電子による量子スピン状態の操作(電磁誘導による量子スピン励起・スピンキラリティーの分割など)など、スピンフラストレーションにより特殊な電気磁気機能を発現する材料の実現を目指す。

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  • 強誘電性・強弾性機能の発現を目指したソフトπ造形システム

    研究課題/領域番号:26102007  2014年7月 - 2019年3月

    日本学術振興会  科学研究費助成事業 新学術領域研究(研究領域提案型)  新学術領域研究(研究領域提案型)

    芥川 智行, 帯刀 陽子, 森 寛敏, 松田 真生, 星野 哲久, 武田 貴志, 菊地 毅光

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    配分額:109330000円 ( 直接経費:84100000円 、 間接経費:25230000円 )

    機能性パイ電子化合物に着目し、強誘電性・強弾性・発光性・電子伝導性などの機能に着目し、ダイナミックまたはエラスティックな性質を有する分子集合体を設計した。プロトン移動、イオン変位や分子回転および反転は、イオン伝導、発光クロミズムや双極子反転を実現し、動的な分子集合体を舞台とした新しい物性化学のフィールドを実現した。ピレン誘導体の発光性強誘電体、ヘリセン誘導体が形成する2次元水素結合系の優れた強誘電体パラメータおよびボウル反転型チアスマネン誘導体のボウル反転型強誘電スイッチング、分子性結晶の強弾性ヒステリシスの測定とそのメカニズムの解明などを研究期間内に実現した。

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  • 超分子ローターによる金属錯体の相転移制御

    2014年4月 - 2017年3月

    日本学術振興会  科学研究費 基盤研究(C) 

    星野 哲久

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    担当区分:研究代表者  資金種別:競争的資金

    スピンクロスオーバーや電荷移動誘起スピン転移(ETCST)、サーモクロミズムや中性-イオン性転移など、金属錯体結晶の相転移では電子とフォノンのカップリングが重要である。本研究では結晶格子中に超分子ローターの回転運動を導入することで、格子振動をチューニングする。具体的には異なるサイズ・対称性をもつ分子ローターの金属錯体塩を合成することで、相転移挙動のコントロールを試みる。また双極子モーメントをもつ分子ローターの導入によって、相転移現象に外部電場依存性を付与する。さらに、金属錯体の相転移に伴う磁性・光学特性・電気的特性をローターの熱運動とカップリングさせることで、分子回転と磁気・電気・光特性が相互に変換可能な系を創出する。

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  • 交差型マルチフェロイック金属錯体の創成

    2012年4月 - 2014年3月

    日本学術振興会  科学研究費 若手研究(B) 

    星野 哲久

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    担当区分:研究代表者  資金種別:競争的資金

    分子回転による巨大誘電応答を示す銅二核錯体をベースとして、回転運動の周波数・対称性・エネルギー障壁・方向性のチューニングにより、転移温度などの強誘電体物性を合理的に制御する。さらに、磁気異方性の大きな金属と架橋配位子の導入による多次元集積化から、高い転移温度を有する強磁性の付与を行う(分子性強誘電-強磁性体)。相互の転移温度が同程度になる分子を設計し、強誘電-強磁性が強くカップリングした、分子性物質として初の交差型マルチフェロイック材料を実現する。

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  • 単分子磁石研究の新展開

    研究課題/領域番号:07J13186  2007年 - 2008年

    日本学術振興会  科学研究費助成事業 特別研究員奨励費  特別研究員奨励費

    星野 哲久

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    配分額:1800000円 ( 直接経費:1800000円 )

    本研究では、高いブロッキング温度を持つ単分子磁石を合成し、量子スピントンネリングについて検討を行うことを目的とした。
    1.前年度では,キラル中心をもつ単一次元鎖磁石を合成した。今年度,新たに有機配位子を光学分割されたものからラセミ体に変更することで,全く構造の異なる鉄・ニッケル四核環状錯体を得ることに成功し,これが単分子磁石であることを明らかにした。すなわち配位子の光学分割の有無だけで,全く異なる構造をもつ単一次元鎖磁石と単分子磁石を選択的に得ることが可能であった。単分子磁石のブロッキング温度はそれほど高くなかったものの,この結果は錯体合成において新たな設計指針を与えるものである。
    2.量子スピントンネリングについては,単分子磁石以外の面からも検討を試みており,前年度は大きなトンネル障壁を持つと予想されている反強磁性的な7員環錯体の合成に成功している。今年度はW.Wernsdorfer教授のグループとの共同研究により,40mKという極低温で磁化測定を行った。その結果,巨視的量子効果による特異な挙動を観測することに成功した。磁化曲線の詳細な解析を行った結果,ゼロ磁場付近のステップは非断熱過程だけでは説明できなかった。これはスピンキラリティーに関連した,量子スピントンネリングの存在を示唆するものである。近々6および8員環錯体について測定を行い,7員環と比較することで,反強磁性的な奇数員環システムの特異性をより明らかにする予定である。

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担当経験のある授業科目(researchmap)

  • 化学特別講義1

    2017年10月
    機関名:東京理科大学

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    科目区分:大学院専門科目 

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  • オムニバス講座

    2012年6月
    機関名:筑波大学

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    科目区分:大学院教養科目 

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  • 応用化学修士研修

    機関名:東北大学

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  • 応用化学博士研修

    機関名:東北大学

     詳細を見る

  • 基礎ゼミ「新しいナノ材料を学ぼう」

    機関名:東北大学

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  • 化学・バイオ工学研修

    機関名:東北大学

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  • 応用化学セミナー

    機関名:東北大学

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  • 化学・バイオ工学卒業研修

    機関名:東北大学

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  • 化学・バイオ工学演習B

    機関名:東北大学

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