研究者データベース

高橋 仁徳(タカハシ キヨノリ)
電子科学研究所 附属グリーンナノテクノロジー研究センター
助教

基本情報

所属

  • 電子科学研究所 附属グリーンナノテクノロジー研究センター

職名

  • 助教

学位

  • 博士(工学)(東北大学)

科研費研究者番号

  • 90812595

ORCID ID

J-Global ID

研究キーワード

  • 固相分子運動   誘電体   ガス吸着   低次元物質   錯体化学   物性化学   

研究分野

  • ナノテク・材料 / 機能物性化学

職歴

  • 2017年08月 - 現在 北海道大学電子科学研究所 附属グリーンナノテクノロジー研究センター 助教
  • 2017年04月 - 2017年07月 北海道大学電子科学研究所 附属グリーンナノテクノロジー研究センター 博士研究員
  • 2016年12月 - 2017年03月 大阪大学大学院理学研究科 附属構造熱科学研究センター 博士研究員
  • 2016年04月 - 2016年12月 国立研究開発法人 産業技術総合研究所 化学プロセス研究部門 機能素材プロセッシンググループ 特別研究員

学歴

  • 2011年04月 - 2016年03月   東北大学   工学研究科   応用化学専攻
  • 2007年04月 - 2011年03月   東北大学   工学部   化学・バイオ工学科

所属学協会

  • 錯体化学会   日本化学会   分子科学会   日本熱測定学会   

研究活動情報

論文

  • Shin-ichiro Noro, Xin Zheng, AnQi Wang, Kazushige Suzuki, Soracha Kosasang, Satoshi Horike, Daniele Padovan, Kiyotaka Nakajima, Hiroyasu Sato, Kiyonori Takahashi, Takayoshi Nakamura
    Inorganic Chemistry 61 8 3379 - 3386 2022年02月28日 [査読有り][通常論文]
  • Ryo Tsunashima, Naomi Fujikawa, Misaki Shiga, Sayu Miyagawa, Shiori Ohno, Atsuko Masuya-Suzuki, Tomoyuki Akutagawa, Kiyonori Takahashi, Takayoshi Nakamura, Sadafumi Nishihara
    CrystEngComm 24 33 5865 - 5869 2022年 
    Slider-crank like force conversion of linear thermal expansion to rotational motion of the coordination chains were observed in the molecular crystal.
  • Xin Chen, Kiyonori Takahashi, Kenta Kokado, Takayoshi Nakamura, Ichiro Hisaki
    MATERIALS ADVANCES 2 17 5639 - 5644 2021年09月 
    To date, proton-conducting organic crystalline materials based on crown ethers have rarely been investigated. In this work, we reveal that flexible organic 18-crown-6 derivatives with one or two 4, 40-dicarboxy-o-terphenyl (CT) groups formed four kinds of crystalline frameworks: 1CT-18C6-I (P2(1)/n), 2CT-18C6-I (P (1) over bar), 2CT-18C6-II (P (1) over bar) and 2CT-18C6-III (Cmc2(1)). Single crystal X-ray diffraction analysis clearly suggested that the water molecules were involved a hydrogen-bonded network for two frameworks. In particular, a unique one-dimensional (1D) water pathway had formed in 2CT-18C6-III and the activation energy was evaluated by Arrhenius plots to be 0.14 eV, indicating that the proton jumps from H3O+ to the neighboring H2O in the hydrogen-bonded network of 2CT-18C6-III.
  • Qin Ji, Kiyonori Takahashi, Shin-ichiro Noro, Yusuke Ishigaki, Kenta Kokado, Takayoshi Nakamura, Ichiro Hisaki
    CRYSTAL GROWTH & DESIGN 21 8 4656 - 4664 2021年08月 
    Hydrogen-bonded organic frameworks (HOFs) composed of high-nitrogen-content p-conjugated molecules are expected to show multifunctionality. In this study, we studied on a HOF based on pyrazinopyrazine (PP), which is one of the simplest and the most essential structural motifs of high-nitrogen-content polycyclic aromatic hydrocarbons. We describe synthesis of a PP-based building block molecule with four carboxyphenyl groups (CP-PP), spectroscopic and electronic properties of CP-PP and its ester precursor, structures of CP-PP-based HOFs, and thermal behaviors of the HOFs. Interestingly, the initial framework with hydrogen-bonded rhombic two-dimesnional (2D) network rapidly undergoes a guest release-induced three-step structural transformation into other frameworks, including a semiopening framework with small void, through rearrangement of hydrogen bonds. These results provide insight into design new functional N pi-HOFs and contribute to solid-state chemistry on porous molecular crystalline materials.
  • Kiyonori Takahashi, Yuji Miyazaki, Shin-ichiro Noro, Motohiro Nakano, Takayoshi Nakamura, Tomoyuki Akutagawa
    DALTON TRANSACTIONS 2021年08月 
    A series of mononuclear Cu-II complexes, [Cu-II(4-FBA)(2)(py)(2)(H2O)] (1), [Cu-II(3-FBA)(2)(py)(2)(H2O)] (2), and (Cu-II(3,4-F(2)BA)(2)(py)(2)(H2O)] (3), where 4-FBA = 4-fluorobenzoate, 3-FBA = 3-fluorobenzoate, 3,4-F(2)BA = 3,4-difluorobenzoate, and py = pyridine, respectively, was synthesized and the complexes crystallographically identified. All the Cu-II complex crystals share a one-dimensional O-H center dot center dot center dot O hydrogen-bonding chain substructure, although the mutual alignment of fluorinated benzoate (F(x)BA) ligands exhibits subtle differences among the various compounds, i.e., F(x)BA ligands align in an antiparallel fashion in crystals 1 and 3, while 3-FBA ligands in crystal 2 are interdigitated with a tilt along the a axis. Reversible phase transitions were found upon heating at 170.7, 171.3, and 267.5 K for crystals 1, 2, and 3, respectively; all crystals showed approximately 3% expansion and shrinkage of the intermolecular O-H center dot center dot center dot O hydrogen bond distances associated with the thermally activated orientational fluctuations of the F(x)BA ligands in crystals 1 and 3. The increase in dielectric constant with increasing temperature, at 240 K, activated molecular fluctuation in the 3,4-F(2)BA ligands in crystal 3. Heat capacity measurements indicated that both the expansion and shrinkage of hydrogen bonds, and the molecular fluctuation in 3,4-F(2)BA ligands, contributed to phase transition, and the latter caused dipole fluctuation, resulting in a dielectric anomaly in crystal 3.
  • Kazuya Kubo, Kiyonori Takahashi, Shota Nakagawa, Ken-ichi Sakai, Shin-ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura
    Crystal Growth & Design 21 4 2340 - 2347 2021年04月07日 [査読有り][通常論文]
     
    Molecular motion within crystals can significantly affect their dielectric properties and functionalities. Crystals of (m-XAni(+)) (DB[18]crown-6) [Ni(dmit)2](-) (m-XAni(+) = m-halogenated anilinium (X = F, 1), (X = Cl, 2), (X = Br, 3), and (X = I, 4); DB[18]crown-6 = dibenzo[18]crown-6; dmit(2-) = 2-thioxio-1,3-dithiol-4,5-dithiolate) were synthesized, and the substituent effects of crystals 2-4 were discussed in terms of crystal structure, dielectric response, and molecular motion compared with crystal 1, which exhibited a ferroelectric transition due to the flip-flop motion of the m-FAni(+) cation. Although crystals 2-4 did not show rotational disorder of the aryl groups due to the larger size of the halogen atoms, in- and out-of-plane pendulum motions were observed. Temperature-dependent crystallographic analysis revealed that crystal 2 underwent a symmetry reduction from space group P2(1)/m at 293 K to P2(1) at 93 K with the disappearance of the mirror plane on m-ClAni(+) associated with the stopping of the out-of-plane pendulum motion. In the case of crystals 3 and 4, an in-plane pendulum motion at small swing angles was suggested, which was further supported by potential energy calculations. Owing to the semiconducting nature of the crystals, these pendulum motions could not be detected by dielectric measurements.
  • Shin-ichiro Noro, Yu Meng, Kazushige Suzuki, Minori Sugiura, Yuh Hijikata, Jenny Pirillo, Xin Zheng, Kiyonori Takahashi, Takayoshi Nakamura
    Inorganic Chemistry 60 7 4531 - 4538 2021年04月05日 [査読有り]
     
    Flexible porous coordination polymers (PCPs)/metal-organic frameworks are unique materials that have potential applications as components of highly efficient separation, sensor, and actuator systems. In general, the structures of flexible PCPs drastically change upon guest loading. In this investigation, we uncovered the rare one-dimensional PCP [Cu-2(bza)(4)(2-apyr)] (1; bza = benzoate and 2-apyr = 2-aminopyrimidine), which exhibits a unique type of flexibility involving temporary pore opening. Single-crystal X-ray diffraction analysis revealed that desolvated 1 and ethyl acetate (AcOEt)-loaded (1.AcOEt) and CO2-loaded (1.CO2) 1 have isolated pores. In the case of 1, the pore structure prevents guest penetration. In addition, the isolated pore structures of 1.AcOEt and 1.CO2 block guest release. However, 1 participates in reversible adsorption/desorption of AcOEt and CO2 because pore opening occurs temporarily. The CO2 adsorption/desorption isotherms of 1 are type I and dissimilar to those observed in traditional flexible PCPs with adsorption/desorption hysteresis. The lesser conventional flexibility displayed by 1 could offer new insight into the design of flexible PCPs.
  • Jiajun Qi, Yuna Kim, Kiyonori Takahashi, Ken'ichi Aoki, Ichiro Hisaki, Takayoshi Nakamura, Nobuyuki Tamaoki
    CHEMISTRY-A EUROPEAN JOURNAL 27 11 3832 - 3841 2021年02月 
    Diacetylene derivatives exhibit solid-state polymerization to polydiacetylene initiated by UV light or gamma-ray irradiation. The activation of the photopolymerization relies on the monomer diynes arrangement. Recently, it has been demonstrated that the first mechanoresponsive bisamide substituted diacetylenes (DAs) show dramatic switching from light-inert to light-reactive states at a given pressure. The origin of this unique phenomenon was apparently related to the pressure-sensitive crystalline transition in DAs, but the molecular mechanism remains elusive. To obtain more insight, herein a series of DAs with varying terminal alkyl spacer length is presented, and their molecular structural effect on the intermolecular hydrogen bonding and steric repulsion is examined. In pristine states, even-parity DAs were inactive upon UV irradiation (lambda=254 nm) unless external pressure was applied. By contrast, odd-parity DAs were easily polymerized upon UV irradiation without pressure application. However, the pressure-induced crystalline phase transition exhibiting photopolymerization was valid for all DAs regardless of their alkyl spacer length. A systematic investigation revealed that the terminal alkyl spacer length, especially its odd/even parity plays a key role in determining the intrinsic intermolecular hydrogen-bonding nature of DA crystals and the resultant molecular packing. In addition, the relevant thermochromic behavior was also observed from photopolymerized polydiacetylenes.
  • Naohiro Hasuo, Kiyonori Takahashi, Ichiro Hisaki, Kenta Kokado, Takayoshi Nakamura
    CrystEngComm 23 14 2756 - 2763 2021年 
    Supramolecular cations, consisting of ethylammonium derivatives (X-CH2CH2-NH3+) complexed with [18] crown-6, were incorporated into [Ni(dmit)(2)](-) crystals in order to promote molecular motion. Crystals of (X-CH2CH2-NH3+)([18]crown-6)[Ni(dmit)(2)](-) (1: X = H, 2: X = F, 3: X = Cl and 4: X = Br) were prepared for this purpose. Although large amplitude molecular motions do not occur in crystal 1, dynamic disorder of F-CH2 groups takes place between two sites in crystal 2. Similar disorder of Cl-CH2 groups along with rotation of [18]crown-6 molecules also exists in crystal 3. Crystal 4 exhibits dynamic disorder of Br-CH2-CH2 groups between four sites. This is especially the case for crystal 4 which undergoes a distinct dielectric response with relaxer-like behavior in the temperature dependence of the dielectric loss tangent. Interactions between [Ni(dmit)(2)](-) ions in all crystals are antiferromagnetic, and the magnitudes of the interactions are qualitatively consistent with the strength of intermolecular interactions estimated from transfer integrals, where interactions within [Ni(dmit)(2)](-) dimers are the larger than the others in all crystals.
  • Makoto Tadokoro, Hironobu Machida, Ryuji Toyofuku, Megumi Murakami, Hajime Kamebuchi, Kyosuke Isoda, Fumiya Kobayashi, Kiyonori Takahashi, Shin'ichiro Noro, Takayoshi Nakamura
    Chemical Communications 57 18 2249 - 2252 2021年 
    [{Re-I(CO)(3)(Hbim)}(3)(tpta)](2) (1, Hbim(-) = 2,2'-biimidazolate monoanion, tpta = 2,4,6-tripyridyl-1,3,5-triazine) was prepared as a nano-space supramolecule by using a new group of H-bonded coordination capsules. The hamburger bun-shaped half unit [{Re-I(CO)(3)(Hbim)}(3)(tpta)] contains six intermolecular H-bonds of Hbim(-) ligands with complementary dual NH center dot center dot center dot N types, and three [Re-I(CO)(3)(Hbim)] are coordinated by bridging tridentate tpta. Interestingly, mechanical grinding easily would convert single crystals of 1 to an amorphous state with minor crystallinity while maintaining the nano-space pores. The ground sample can reversibly uptake and release small molecules such as CO2 and (CH2Cl)(2).
  • Yoshimitsu Sagara, Kiyonori Takahashi, Atsushi Seki, Tatsuya Muramatsu, Takayoshi Nakamura, Nobuyuki Tamaoki
    Journal of Materials Chemistry C 9 5 1671 - 1677 2021年 
    Achieving multiple mechanoresponsive luminescence-related functions from a single molecule remains challenging. Here, we demonstrate that both two-step mechanoresponsive luminescence and the release of small guest molecules are achieved by a 9,10-bis(phenylethynyl)anthracene-based cyclophane. When gently crushed, the yellow-emissive crystal of the cyclophane exhibits a hypsochromic shift of the emission band, because of alterations in molecular packing at the surface. Subsequent grinding results in a bathochromic shift of the emission band due to excimer formation accompanying the transition from the crystalline state to an amorphous state. Another pseudopolymorph of the cyclophane exhibits the release of chloroform from its crystal structure in response to mechanical stimuli, accompanied by a photoluminescent color change from yellow-green to yellow. These results reveal that luminescent cyclophanes are promising candidates for creating sophisticated mechanoresponsive luminescent materials.
  • Kilingaru I. Shivakumar, Shin-ichiro Noro, Yuna Yamaguchi, Yusuke Ishigaki, Akinori Saeki, Kiyonori Takahashi, Takayoshi Nakamura, Ichiro Hisaki
    Chemical Communications 57 9 1157 - 1160 2021年 
    Redox-active hexakis(4-carboxyphenyl) tri(dithiolylidene)cyclohexanetrione (CPDC) was synthesized. The CPDC-based porous framework, constructed via anomalistic helical hydrogen-bonding, exhibites permanent porosity and photoconductivity.
  • Masaru Fujibayashi, Yu Watari, Ryo Tsunashima, Sadafumi Nishihara, Shin-ichiro Noro, Chang-Gen Lin, Yu-Fei Song, Kiyonori Takahashi, Takayoshi Nakamura, Tomoyuki Akutagawa
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 59 50 22446 - 22450 2020年12月 
    The structural phase of a metal oxide changes with temperature and pressure. During phase transitions, component ions move in multidimensional metal-oxygen networks. Such macroscopic structural events are robust to changes in particle size, even at scales of around 10 nm, and size effects limiting these transitions are particularly important in, for example, high-density memory applications of ferroelectrics. In this study, we examined structural transitions of the molecular metal oxide [Na@(SO3)(2)(n-BuPO3)(4)(Mo4Mo14O49)-Mo-V-O-VI](5-)(Molecule1) at approximately 2 nm by using single-crystal X-ray diffraction analysis. The Na(+)encapsulated in the discrete metal-oxide anion exhibited a reversible order-disorder transition with distortion of the Mo-O molecular framework induced by temperature. Similar order-disorder transitions were also triggered by chemical pressure induced by removing crystalline solvent molecules in the single-crystal state or by substituting the countercation to change the molecular packing.
  • Xin Zheng, Katsuo Fukuhara, Yuh Hijikata, Jenny Pirillo, Hiroyasu Sato, Kiyonori Takahashi, Shin-ichiro Noro, Takayoshi Nakamura
    COMMUNICATIONS CHEMISTRY 3 1 2020年10月 
    The selective carbon dioxide (CO2) absorption properties of ionic liquids (ILs) are highly pertinent to the development of methods to capture CO2. Although it has been reported that fluorinated components give ILs enhanced CO2 solubilities, it has been challenging to gain a deep understanding of the interactions occurring between ILs and CO2. In this investigation, we have utilized the soft crystalline material [Cu(NTf2)(2)(bpp)(2)] (NTf2- = bis(trifluoromethylsulfonyl)imide, bpp = 1,3-bis-(4-pyridyl)propane) as a surrogate for single-crystal X-ray diffraction analysis to visualize interactions occurring between CO2 and NTf2-, the fluorinated IL component that is responsible for high CO2 solubility. Analysis of the structure of a CO2-loaded crystal reveals that CO2 interacts with both fluorine and oxygen atoms of NTf2- anions in a trans rather than cis conformation about the S-N bond. Theoretical analysis of the structure of the CO2-loaded crystal indicates that dispersion and electrostatic interactions exist between CO2 and the framework. The overall results provide important insight into understanding and improving the CO2 absorption properties of ILs.The selective CO2 absorption properties of ionic liquids make them attractive for CO2 capture purposes, but their tendency to crystallize poorly hampers structural investigations. Here a soft crystalline material is used as a surrogate for single-crystal X-ray diffraction analysis to visualize interactions between CO2 and NTf2-, the fluorinated component that is responsible for high CO2 solubility.
  • Yoshimitsu Sagara, Kiyonori Takahashi, Takayoshi Nakamura, Nobuyuki Tamaoki
    JOURNAL OF MATERIALS CHEMISTRY C 8 29 10039 - 10046 2020年08月 [査読有り][通常論文]
     
    Luminescent materials that change their photophysical properties and molecular arrangement in response to external stimuli have attracted attention because of the potential application in sensors, memory, security inks, and informational displays. The combination of external stimuli-responsive luminescence with the release of volatile molecules would give more sophisticated photofunctional materials. Herein we discuss a 9,10-bis(phenylethynyl)anthracene derivative that formed green-emissive crystals containing one-dimensional toluene channels. Amide groups of the compounds formed linear hydrogen-bonds in the crystals. Thermal treatment resulted in a phase transition to another crystalline state with the release of the guest toluene molecules. However, little alteration in the photoluminescent properties occurred during the transition. Mechanical stimuli led to the release of volatile molecules along with an emission colour change with a transition from the crystalline to an amorphous phase. Infrared spectroscopy showed that linear hydrogen bonds remained after a thermal treatment-induced phase transition, whereas mechanical stimuli disturbed them.
  • Xin Zheng, Hiroyasu Sato, Kiyonori Takahashi, Shin-ichiro Noro, Takayoshi Nakamura
    CRYSTAL GROWTH & DESIGN 20 6 3596 - 3600 2020年06月 [査読有り][通常論文]
     
    Porous materials possessing fluid spaces are of great interest in the field of material science because they have the capability of undergoing unique, external stimuli-promoted and guest uptake/release-responsive changes in shapes and sizes. Polymethylene chains are postulated to be important components in metal-organic frameworks (MOFs) enabling them to possess fluid spaces. The three-dimensional (3D) cationic MOF, [Cu-(bib)(2.5)] (bib = 1,4-bisimidazole butane), which contains organic bridging ligands with conformationally flexible tetramethylene ((CH2)(4)) units, was designed to assess this proposal. The combined results of DSC measurements, single-crystal X-ray diffraction analysis, and impedance spectroscopy demonstrate that this MOF encapsulating bis(trifluoromethylsulfonyl)amide (NTf2-) anions contains fluid space and that it undergoes a crystal-to-crystal transition in association with a synchronous change in the conformations of both the bib ligand, caused by C-C bond rotation, and the NTf2- anion stemming from rotation about the N-S bond.
  • Kiyonori Takahashi
    Chemistry – An Asian Journal 2020年02月17日
  • Simin Li, Kiyonori Takahashi, Ichiro Hisaki, Kenta Kokado, Takayoshi Nakamura
    Dalton Transactions 49 46 16772 - 16777 2020年 
    Crystals of (HDABCO(+))(9)(DABCO)[Ni(dmit)(2)](9)center dot 6CH(3)CN were shown to have a space group of R3, a hexapetal flower-like channel of [Ni(dmit)(2)] anions, and a one-dimensional hydrogen bonding chain composed of protonated DABCO and CH3CN molecules. The crystals display antiferromagnetic and ferromagnetic interactions within and between hexamers, respectively, whereas the flexible DABCO-CH3CN array shows dielectric relaxation.
  • Horii, Y., Kanegae, Y., Takahashi, K., Fuyuhiro, A., Noguchi, M., Suzuki, H., Nakano, M.
    Inorganic Chemistry 59 8 5418 - 5423 2020年 [査読有り][通常論文]
     
    Two crystal polymorphs of Ni(cyclam)I-2 (cyclam = 1,4,8,11-tetraazacyclotetradecane) were synthesized, and their magnetic properties were investigated. Temperature-dependent X-ray structural analysis and magnetic measurements revealed gradual spin transition in molecular-crystal polymorph trans-[Ni(cyclam)I-2] (1a), whereas the zigzag-chain polymorph catena-[Ni(cyclam)(mu-I)]I (1b) did not show an obvious spin transition. The entropy difference between high- and low-spin states of la estimated by assuming the spin-equilibrium model is much smaller than those in typical iron(II)-based spin-crossover (SCO) complexes, suggesting that the normal mode softening is less remarkable in la. In this system, it is clearly evidenced that the interaction mode responsible to the spin equilibrium in octahedral nickel(II) complexes is highly anistropic, i.e., z-elongation and x,y-shortening of the coordination octahedron.
  • Hisaki, I., Ji, Q., Takahashi, K., Tohnai, N., Nakamura, T.
    Crystal Growth and Design 20 5 3190 - 3198 2020年 [査読有り][通常論文]
     
    A porous hydrogen-bonded organic framework (HOF) composed of N-hetero pi-conjugated molecules (N pi-HOF) is a promising candidate for multifunctional porous materials. However, such HOFs are still limited and only a handful of examples have been reported. In this study, we investigated the positional effects of annelated pyrazine rings on the structure and stability of N pi-HOFs to establish a design principle for N pi-HOFs. A new isomer of hexaazatrinaphthylene (CPBTQ) was synthesized and subjected to N pi-HOF construction, activation, and an evaluation of stability and permanent porosity. A comparison between two kinds of N pi-HOFs composed of isomers (CPBTQ and CPHATN) possessing three pyrazine rings annelated at different positions indicates that the positional difference of the pyrazine rings strongly affects the conformation of the peripheral phenylene groups, which then leads to different structures and stabilities of the N pi-HOFs. The activated N pi-HOF composed of CPBTQ (CPBTQ-1a) is revealed to exhibit a Brunauer-Emmett-Teller surface area of 471 m(2) g(-1) and shows HCl responsiveness thanks to the basic pyrazine rings annelated to the triphenylene core. We believe that the present results can contribute not only to the construction of multifunctional porous materials but also to the chemistry of heteroaromatic compounds.
  • Sagara, Y., Takahashi, K., Nakamura, T., Tamaoki, N.
    Molecular Systems Design and Engineering 5 1 205 - 211 2020年 [査読有り][通常論文]
     

    The crystal structure of a cyclophane that exhibits a supercooled nematic phase and thermoresponsive luminescence was solved.

  • Sagara, Y., Takahashi, K., Nakamura, T., Tamaoki, N.
    Chemistry - An Asian Journal 15 4 478 - 482 2020年 [査読有り][通常論文]
     
    Introduction of functional groups that can form intermolecular hydrogen bonds into highly-emissive luminophores is a promising way to induce mechanochromic luminescence. Herein, we report that a 9,10-bis(phenylethynyl)anthracene derivative featuring two amide groups forms green-emissive crystals based on two-dimensional hydrogen-bonded molecular sheets. Mechanical grinding changed the emission from green to yellow, owing to a transition from a crystalline to an amorphous phase. Infrared spectroscopy revealed that mechanical stimuli disrupted the linear hydrogen-bonding formation. A thermal treatment recovered the original green photoluminescence.
  • Ichiro Hisaki, Xin Chen, Kiyonori Takahashi, Takayoshi Nakamura
    Angewandte Chemie (International ed. in English) 58 42 14794 - 14794 2019年10月14日
  • 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 123 38 23545 - 23553 2019年09月 [査読有り][通常論文]
     
    Hydrophilic fullerene derivatives of C-60(OH)(12) (1) and C-60(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 center dot center dot center dot O hydrogen-bonding networks in amorphous 1 and 2 produced extrinsic adsorption-desorption pores with a hydrophilic environment posed by -OH groups, where N-2, CO2, H-2, 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 center dot center dot center dot O hydrogen-bonding networks. The Brunauer-Emmett-Teller (BET) specific surface areas of amorphous 1 and 2 were 315 and 351 m(2) 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.
  • 久木一朗, 高橋仁徳, 中村貴義
    有機合成化学協会誌 77 7 706 - 715 2019年 [査読有り][通常論文]
     
    Among porous molecular crystals that are formed via self-assembly of organic molecules, those constructed through preorganized hydrogen bonds, named hydrogen-bonded organic frameworks (HOFs), recently attract much attention as new porous organic materials because of their high crystallinity, potential designability, and facile construction process. HOFs, however, are relatively fragile and their current designing strategy is still insufficient compared with other porous materials such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) because of weakness of H-bonds. Stable HOFs with permanent porosity have been required. In connection with this, we have demonstrated that various C-3-symmetric pi-conjugated molecules possessing o-bis (4-carboxyphenyl) aryl groups in their periphery successfully gave H-bonding low-density networked structures, which effectively gave stable HOFs with permanent porosity by activation (removal of included solvent molecules). The obtained HOFs show significant thermal stability over 300 degrees C and permanent porosity with the Brunauer-Emmett-Teller (BET) surface area values up to 1288 m(2)g(-1). The frameworks also can work as a platform to achieve very unique alignment of functional molecules such as C-60 Moreover, optelectronic properties of pi-conjugated systems applied for the building blocks enabled to provide multifunctional HOFs such as acid-responsive HOFs with permanent porosity. Our strategy for constructing functional HOFs contribute to developing a new field of porous organic materials.
  • Islam, M.J., Yuyama, K.-I., Takahashi, K., Nakamura, T., Konishi, K., Biju, V.
    NPG Asia Materials 11 1 31  2019年 [査読有り][通常論文]
     
    The development of new methods to engineer lead halide perovskite crystals with a controlled band gap and emission properties is an active subject in materials science and chemistry. We present the preparation of mixed-halide lead perovskites by spatially- and temporally- controlled chemical reactions and crystal growth under an optical potential in unsaturated precursor solutions. The crystals are characterized by transmission and photoluminescence spectral measurements and X-ray diffraction analysis. When compared with the spontaneous formation of multiple crystals in saturated precursor solutions, the optical potential creates large single crystals with a high chloride composition, providing distinct blue and green fluorescent crystals of chloride-bromide lead perovskites. We discuss the formation of mixed-halide perovskites from the viewpoints of an increased rate of chemical reaction via the formation and desolvation of precursor complexes and a decreased free energy potential.
  • Hisaki, I., Xin, C., Takahashi, K., Nakamura, T.
    Angewandte Chemie - International Edition 58 33 11160 - 11170 2019年 [査読有り][通常論文]
     
    Designing organic components that can be used to construct porous materials enables the preparation of tailored functionalized materials. Research into porous materials has seen a resurgence in the past decade as a result of finding of self-standing porous molecular crystals (PMCs). Particularly, a number of crystalline systems with permanent porosity that are formed by self-assembly through hydrogen bonding (H-bonding) have been developed. Such systems are called hydrogen-bonded organic frameworks (HOFs). Herein we systematically describe H-bonding patterns (supramolecular synthons) and molecular structures (tectons) that have been used to achieve thermal and chemical durability, a large surface area, and functions, such as selective gas sorption and separation, which can provide design principles for constructing HOFs with permanent porosity.
  • Shirakawa, Y., Takahashi, K., Sato, H., Hoshino, N., Anetai, H., Noro, S.-I., Akutagawa, T., Nakamura, T.
    Chemistry - A European Journal 25 28 6920 - 6927 2019年 [査読有り][通常論文]
     
    The pseudo-polyrotaxane structure of [(H-bpy(+))(DB-24-crown-8)](infinity) (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 center dot center dot center dot 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)](-).
  • Ghimire, S., Chouhan, L., Takano, Y., Takahashi, K., Nakamura, T., Yuyama, K.-I., Biju, V.
    ACS Energy Letters 4 1 133 - 141 2019年 [査読有り][通常論文]
     
    Lead halide perovskites are promising for energy harvesting and lighting applications. We show amplified emission from films of organic-inorganic or all-inorganic lead halide perovskite nanocrystals. Also, multicolor emission is detected from interfacial layers of chloride and bromide perovskites. While amplified emission originates from spatial confinement of manifold charge carriers in films, multicolor emission emanates from interfacial halogen-exchanged layers. In a film, the amplified emission is averaged over a large number of nanocrystals, which prevents us from detecting any spectral narrowing. Conversely, amplified spontaneous emission (ASE) and spectral narrowing are detected from an isolated perovskite microcrystal. Interestingly, under low-intensity excitation, a perovskite nanocrystal film shows unusually delayed emission, which becomes extremely fast and spatially confined at higher intensities of excitation light. By precisely detecting photoluminescence from an irradiated area and outside, we reveal the migration as well as confinement of photogenerated charge carriers in the film. The migration of charge carriers is more efficient in a film of organic-inorganic perovskites than that in all-inorganic perovskites.
  • Ghimire, S., Takahashi, K., Takano, Y., Nakamura, T., Biju, V.
    Journal of Physical Chemistry C 123 45 27752 - 27758 2019年 [査読有り][通常論文]
     
    Photon recycling by multiple reabsorption-emission is responsible for the long-range energy transport in large crystals and thick films of lead halide perovskites, resulting in red-shifted and delayed emission. Apart from such a radiative process, nonradiative energy transfer influences photon recycling in perovskites with close-packed donor-acceptor-type states. In this study, we report the role of nonradiative energy transfer on photon recycling in piezochemically synthesized and close-packed pure and mixed halide methylammonium lead perovskites. Here, the pressure applied to precursors of perovskites helps us to synthesize and close-pack perovskite crystallites into pellets. Nonetheless, interestingly, we find that the applied pressure redistributes the emission maxima or band- gap of these perovskites. The temporally and spectrally resolved photoluminescence from the mixed halide sample unveils nonradiative energy transfer from a higher (bromide) to a lower (iodide) band-gap domain, where the rate of relaxation of the bromide domain is higher than that of the pure bromide perovskite. These results help us to confirm the role of nonradiative energy transfer on photon recycling in perovskites.
  • Ken-ichi Yuyama, Md Jahidul Islam, Kiyonori Takahashi, Takayoshi Nakamura, Vasudevanpillai Biju
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 57 41 13424 - 13428 2018年10月 [査読有り][通常論文]
     
    Single crystals of organolead halide perovskites attract much attention to electrooptical and photovoltaic applications. They are usually prepared in precursor solutions incubated at controlled temperatures or under optimized vapor atmosphere conditions, and thus, multiple perovskite crystals are nucleated all over the solution. Multiple nucleation of crystals prevents efficient use of precursors in the preferential growth of large single crystals. An innovative approach is presented for spatiotemporally controlled, selective nucleation and growth of single crystals of lead halide perovskites by optical trapping with a focused laser beam. Upon such trapping in unsaturated precursor solutions, nucleation of MAPbX(3) (MA = CH3NH3+; X = Cl-, Br-, or I-) is induced at the focal spot through increase in the concentration of perovskite precursors in the focal volume. The rate at which the nucleated crystal grows depends upon whether the perovskite absorbs the trapping laser or not. These findings suggest that optical trapping would be useful to prepare various perovskite single crystals and modify their optical and electronic properties; thereby, offering new methods for engineering of perovskite crystals.
  • Hiroshi Nishiyama, Takashi Takeda, Norihisa Hoshino, Kiyonori Takahashi, Shin-ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa
    Crystal Growth & Design 18 1 286 - 296 2018年 [査読有り][通常論文]
     
    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 center dot(guest) or 1 center dot(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 center dot(THF)(2) and 1 center dot(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 center dot(guest) 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 center dot center dot center dot 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 pi-stacking and/or S center dot center dot center dot S interactions. Alternating layers of N-H center dot center dot center dot 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.
  • Masaru Kato, Kazuya Ogura, Shogo Nakagawa, Shoichi Tokuda, Kiyonori Takahashi, Takayoshi Nakamura, Ichizo Yagi
    ACS Omega 3 8 9052 - 9059 2018年 [査読有り][通常論文]
     
    Pt-based nanostructured electrocatalysts supported on carbon black have been widely studied for the oxygen reduction reaction (ORR), which occurs at the cathode in polymer electrolyte fuel cells. Because sluggish ORR kinetics are known to govern the cell performance, there is a need to develop highly active and durable electrocatalysts. The ORR activity of Pt-based electrocatalysts can be improved by controlling their morphology and alloying Pt with transition metals such as Ni. Improving the catalyst durability remains challenging and there is a lack of catalyst design concepts and synthetic strategies. We report the enhancement of the ORR activity and durability of a nanostructured Pt-Ni electrocatalyst by strong metal/support interactions with a nitrogen-doped carbon (NC) support. Pt-Ni rhombic dodecahedral nanoframes (NFs) were immobilized on the NC support and showed higher ORR electrocatalytic activity and durability in acidic media than that supported on a nondoped carbon black. Durability tests demonstrated that NF/NC showed almost no activity loss even after 50 000 potential cycles under catalytic conditions, and the Ni dissolution from the NFs was suppressed at the NC support, as confirmed by, energy dispersive X-ray spectroscopy analysis. Physicochemical measurements including surface-enhanced infrared absorption spectroscopy of surface-adsorbed CO revealed that the strong metal/support interactions of the NF with the NC support caused the downshift of the d-band center position of the surface Pt. Our findings demonstrate that tuning the electronic structure of nanostructured Pt alloy electrocatalysts via the strong metal/support interactions with heteroatom-doped carbon supports will allow the development of highly active and robust electrocatalysts.
  • 高橋仁徳, 石井亮, 鈴木麻実, 中村孝志, 吉田学, 蛯名武雄
    Clay Science 21 1 1 - 6 2017年06月 [査読有り][通常論文]
  • Kiyonori Takahashi, Ryo Ishii, Takashi Nakamura, Asami Suzuki, Takeo Ebina, Manabu Yoshida, Munehiro Kubota, Thi Thi Nge, Tatsuhiko Yamada
    ADVANCED MATERIALS 29 17 2017年05月 [査読有り][通常論文]
     
    Requirements for flexible electronic substrate are successfully accomplished by green nanocomposite film fabricated with two natural components: glycol-modified biomass lignin and Li+ montmorillonite clay. In addition to these major components, a cross-linking polymer between the lignin is incorporated into montmorillonite. Multilayer-assembled structure is formed due to stacking nature of high aspect montmorillonite, resulting in thermal durability up to 573 K, low thermal expansion, and oxygen barrier property below measurable limit. Preannealing for montmorillonite and the cross-linking formation enhance moisture barrier property superior to that of industrial engineering plastics, polyimide. As a result, the film has advantages for electronic film substrate. Furthermore, these properties can be achieved at the drying temperature up to 503 K, while the polyimide films are difficult to fabricate by this temperature. In order to examine its applicability for substrate film, flexible electrodes are finely printed on it and touch sensor device can be constructed with rigid elements on the electrode. In consequence, this nanocomposite film is expected to contribute to production of functional materials, progresses in expansion of biomass usage with low energy consumption, and construction of environmental friendly flexible electronic devices.
  • 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 [査読有り][通常論文]
     
    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)](8), 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 inter-chain 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)]8 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)center dot center dot center dot pi and multipoint C-H center dot center dot center dot pi 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-CH(3)BA)(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.
  • Kiyonori Takahashi, Norihisa Hoshino, Takashi Takeda, Shin-ichiro Noro, Takayoshi Nakamura, Sadamu Takeda, Tomoyuki Akutagawa
    INORGANIC CHEMISTRY 54 19 9423 - 9431 2015年10月 [査読有り][通常論文]
     
    CO2 and N-2 gas adsorption/desorption properties of one-dimensional copper(II) polymers with paddle-wheel units [Cu-2(II)(p-XBA)(4)(pyrazine)(infinity) 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 OCH3). 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 CO2 (T = 195 K) and N-2 (T = 77 K), with differences depending on the precise substituent. van der Waals interchain interactions, specifically pi center dot center dot center dot pi, halogen center dot center dot center dot pi, and C-H center dot center dot center dot pi 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 CO2 and N-2 gases.
  • Endo, M., Nakane, Y., Takahashi, K., Hoshino, N., Takeda, T., Noro, S.-I., Nakamura, T., Akutagawa, T.
    Journal of Physical Chemistry B 119 4 1768 - 1777 2015年 [査読有り][通常論文]
     
    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 center dot(H2O), 2 center dot(H2O), 3 center dot 0.5(H2O), 4 center dot(H2O), and 5 center dot(H2O); they were then converted into dehydrated forms by increasing the temperature to similar 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 p-stacking columnar structure in the hydrated crystals, while one- or two-dimensional M+similar to O networks were observed in the inorganic layers. Our results showed that the M+similar to O interactions and their connectivity are strongly influenced by the size of the cations. The reconstruction of the M+similar to 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.
  • Kiyonori Takahashi, Norihisa Hoshino, Shin-Ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa
    SCIENCE OF ADVANCED MATERIALS 6 7 1417 - 1424 2014年07月 [査読有り][通常論文]
     
    Cu(II) binuclear coordination polymers of [Cu(II)(ADCOO)(4)(pz)](infinity) (1), [Cu(II)(ADCOO)(4)(F-pz)](infinity) (2), and [Cu(II)(Cl-ADCOO)(4)(pz)](infinity) (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)](infinity) 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.
  • Kiyonori Takahashi, Norihisa Hoshino, Takashi Takeda, Shin-ichiro Noro, Takayoshi Nakamura, Sadamu Takeda, Tomoyuki Akutagawa
    DALTON TRANSACTIONS 43 24 9081 - 9089 2014年 [査読有り][通常論文]
     
    m-Fluorobenzoate (m-FBA), 2,3-difluorobenzoate (2,3-F(2)BA), 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)](infinity) (1), [Cu(II)(2)(2,3-F(2)BA)(4)(pz)](infinity) (2), [Cu(II)(2)(m-MBA)(4)(pz)](infinity) (3), and [Cu(II)(2)(m-ClBA)(4)(pz)](infinity) (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 center dot 4CH(3)CN, 2 center dot 4CH(3)CN, 3 center dot 2CH(3)CN, and 4 center dot 2CH(3)CN. Both pi-dimer and dipole-dipole interactions were simultaneously observed in the interchain interactions of m-FBA and/or 2,3-F(2)BA 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 H2O 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 CO2 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.
  • Takahashi, K., Hoshino, N., Kubo, K., Nakamura, T., Akutagawa, T.
    CrystEngComm 14 16 5235 - 5241 2012年 [査読有り][通常論文]
     
    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)](-)center dot(CH3CN)(0.25) (1). The pi-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 CH3CN 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)]center dot(CH3CN)(CH3OH) (3). The orientational disorder of the F-sites of m-FAni(+) in crystal 1 was associated with the presence of the CH3CN molecule, which was different from the twofold 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 pi-stacking structure of anions in 1 decreased its thermal stability.
  • 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 [査読有り][通常論文]
     
    The temperature-dependent dynamic properties of [Cu-2(II)(ADCOO)(4)(DMF)(2)]center dot(DMF)(2) (1) and [Cu-2(II)(ADCOO)(4)(AcOEt)(2)] (2) crystals were examined by X-ray crystallography, H-1 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-2(II)(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-2(II)(ADCOO)(4)] moiety, forming [Cu-2(II)-(ADCOO)(4)(DMF)(2)] and [Cu-2(II)(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 in-creasing 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).
  • Kiyonori Takahashi, Naoko Ogawa, Hiromasa Oku, Koichi Hashimoto
    2006 IEEE INTERNATIONAL CONFERENCE ON ROBOTICS AND AUTOMATION (ICRA), VOLS 1-10 1408 - + 2006年 
    We propose a novel method to control a lot of microorganisms by using visual feedback for micro-robotic application. Our goal is to control a cluster of microorganisms as micro-scale smart robots for various applications, since microorganisms have efficient actuators and accurate sensors. Compared with single-cell level actuation methods proposed before, this method has the following advantages: (1) A cluster of microorganisms can cancel stochastic perturbations of behavior by taking the average; (2) A cluster of microorganisms can be more powerful than a single microorganism, and thus it can perform a variety of tasks. A visual feedback system is constructed to control cells using galvanotaxis (response to the electric field). Experimental results show the feasibility of visual feedback control of a paramecium cell cluster. In addition, Micro-manipulation of small objects by the cell cluster is also demonstrated.

その他活動・業績

特許

受賞

  • 2018年09月 日本粘土科学会 平成30年度論文賞
     Preparation of Lignin/Montmorillonite Nanocomposite Films and Its Characterization for Electronic Devices 
    受賞者: 高橋仁徳;石井亮;鈴木麻実;中村孝志;吉田学;蛯名武雄
  • 2016年03月 東北大学 総長賞
  • 2015年09月 錯体化学会 RSC CrystEngCommポスター賞
     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 
    受賞者: 高橋 仁徳;星野 哲久;野呂 真一郎;中村 貴義;芥川 智行
  • 2015年08月 錯体化学若手の会 ポスター賞
     ピラジン架橋一次元鎖Cu錯体のHirshfeld表面解析による構造柔軟性の評価 
    受賞者: 高橋仁徳;星野哲久;野呂真一郎;中村貴義;芥川智行
  • 2014年04月 日本化学会 低次元系光機能材料研究会 優秀講演賞
     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 
    受賞者: 高橋仁徳;星野哲久;野呂真一郎;中村貴義;芥川智行
  • 2013年09月 日本化学会東北支部 ポスター賞
     Structural Changes and Physical Properties of Copper(II) Complex by Pyridine Chemsorption 
    受賞者: 高橋仁徳;星野哲久;野呂真一郎;中村貴義;芥川智行

共同研究・競争的資金等の研究課題

  • 擬ロタキサン型超分子カチオンを用いた固相分子機械の機能開拓
    日本学術振興会:科学研究費助成事業 若手研究
    研究期間 : 2021年04月 -2023年03月 
    代表者 : 高橋 仁徳
  • 分子水車機構に基づく水の能動輸送と水素同位体分離
    ハーモニック伊藤財団:研究助成
    研究期間 : 2022年04月 -2023年03月
  • 分子性電子材料における熱膨張制御と負の熱膨張が駆動する電気磁気物性
    公益財団法人 池谷科学技術振興財団:研究助成
    研究期間 : 2022年04月 -2023年03月
  • 放射性トリチウム水分離に向けた分子回転型水分子リレー輸送による水/重水分離材の開拓と分離機構解明
    公益財団法人日本科学協会:笹川科学研究助成
    研究期間 : 2021年04月 -2022年02月
  • 超分子の動的性質を利用した分子性交差型マルチフエロイック材料 の開拓
    公益財団法人 村田学術振興財団:研究助成
    研究期間 : 2021年01月 -2021年12月
  • 融解するイオンラジカル分子導体・半導体の開発と中間相・相境界近傍での機能開拓
    日本学術振興会:科学研究費助成事業 若手研究
    研究期間 : 2019年04月 -2021年03月 
    代表者 : 高橋 仁徳
     
    融解するアニオンラジカル塩のライブラリ構築を目的に、[Ni(dmit)2]- (dmit2- = 11,3-dithiole-2-thione-4,5-dithiolate)およびdibenzo[24]crown-8 (DB24C8) をそれぞれアニオン、ホスト分子として固定し、カチオンとして、様々なアルキル鎖長を持つイミダゾリウムおよびピリジニウム誘導体を導入した塩を作製した。 得られた結晶の単結晶X線構造解析より、カチオンのアルキル鎖長が3以下の場合、DB24C8が1次元のカラム構造を形成し、カチオンをDB24C8の環内に完全に包接した結晶が得られた。熱重量示差熱測定 (TG-DTA) より、熱的に安定な420 K以下に融解に対応するピークを示した。アルキル鎖長の長いカチオンを導入すると、組成比の異なる結晶が得られ、融点は単調に減少しなかったことから、融点の制御にはカチオンのアルキル鎖長だけではなく、結晶構造を含めた分子設計が必要であるといえる。 ITO電極に微結晶試料をはさみ、交流伝導度の温度―周波数依存性を測定した。室温から融点以下の固相において、交流伝導度は温度上昇に伴って上昇し、低周波数域には周波数に依存しないプラトーを示した。交流伝導度は、周波数に依存しない直流伝導成分と、周波数のべき乗に依存する伝導成分の足し合わせで記述できることから、直流伝導成分は[Ni(dmit)2]- に由来する半導体電子伝導であると考えられる。一方、融解後の液相では、高周波数域で交流伝導度はほぼ一定値だったが、低周波数になるにつれて、交流伝導度が減少していく挙動が見られた。これは電極分極効果によって,電極界面へのイオンの移動が生じ、空間電荷領域を形成したためと考えられる。液相では、イオン伝導を示すことと対応しているといえる。
  • 配位高分子の構造変化を用いた選択的・高感度ガスセンサーの開発
    ノーステック財団:若手研究人材・ネットワーク育成補助金
    研究期間 : 2018年08月 -2019年02月
  • 日本学術振興会:科学研究費助成事業 特別研究員奨励費
    研究期間 : 2013年04月 -2016年03月 
    代表者 : 高橋 仁徳
     
    ガスの吸脱着をバイアスとした分子運動と強誘電物性の融合システムの開発にかかわる新たな分子設計を見出すことを目的とし、配位子間の水素結合によって一次元鎖を形成する単核Cu錯体を研究対象とした。ベンゾアート誘導体配位子(RBA)の置換基による分子間相互作用の設計によって1) 極性結晶化による第二次高調波発生(SHG)の応答が可能な錯体結晶および、2) 配位子による分子運動が可能な錯体結晶の作製が可能であると着想し、各種実験を行った。
    1)単結晶X線結晶構造解析より、隣接するRBAの酸素原子とH2O配位子間で分子間水素結合による極性1次元鎖構造の形成が確認された。鎖間はpyridineの水素原子とRBAの酸素原子間の弱い水素結合相互作用により、2次元レイヤー構造を形成していた。さらに、レイヤー同士の双極子モーメントが同じ向きに並行にパッキングする場合に、極性結晶が出現した。RBAの置換基の設計は極性レイヤー間の分子間相互作用の制御を可能とし、比較的強い分子間相互作用が極性配列を安定化させた。4つの極性結晶のSHG強度は、グラニュー糖比で約0.7程度であった。
    2)フッ素基をRBAの置換基として有する3種類の単核Cu錯体結晶に対して、示差走査熱量測定および転移前後におけるX線回折パターンの変化を検討し、構造相転移を示すことを明らかにした。転移前後での結晶構造解析からRBAの芳香環の配向が揺らいでおり、特に置換基が3,4-F2の結晶は3-位のF基が秩序-無秩序型の構造変化を示した。誘電率e1の温度-周波数依存性測定で、R = 3,4-F2の結晶のみ相転移後の誘電率e1の上昇がみられ、構造変化と対応していた。R = 3,4-F2の結晶では4-位のF基による双極子―双極子相互作用が有効に働き、分子運動を可能とする分子配列を実現したと考えられる。

教育活動情報

主要な担当授業

  • 一般教育演習(フレッシュマンセミナー)
    開講年度 : 2021年
    課程区分 : 学士課程
    開講学部 : 全学教育
    キーワード : 日常生活、キッチン、コーヒー、原生生物、色

大学運営

委員歴

  • 2021年10月 - 現在   日本熱測定学会   委員   学会誌「熱測定」編集委員
  • 2019年04月 - 現在   有機固体若手の会   有機固体若手の会 2019冬の学校 世話人
  • 2018年04月 - 現在   錯体化学若手の会   北海道・東北支部 世話人


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