Researchers Database

TAKASE, Masayoshi

    Graduate School of Science and Engineering Engineering for Production and Environment Associate Professor
Last Updated :2020/10/13

Researcher Information

Research funding number

  • 90516121


J-Global ID

Research Interests

  • 含窒素グラフェン   π電子共役系   グラフェン   テトラチアフルバレン   超分子集合体   自己組織化   構造有機化学   放射状ドナー分子   分子ワイヤー   ナノ分子   包接錯体   らせん構造   

Research Areas

  • Life sciences / Bioorganic chemistry
  • Nanotechnology/Materials / Structural/physical organic chemistry

Academic & Professional Experience

  • 2015/01 - Today  Ehime UniversityGraduate School of Science and EngineeringAssociate Professor
  • 2015/04 - 2016/03  Kyushu UniversityInstitute for Materials Chemistry and Engineering非常勤講師
  • 2015/01 - 2016/03  Tokyo Metropolitan University客員准教授
  • 2008/01 - 2014/12  Tokyo Metropolitan UniversityGraduate School of Science and EngineeringAssistant Professor
  • 2004/10 - 2007/12  Max-Planck-Institute for Polymer ResearchResearch fellowship of Alexander von Humboldt
  • 2003/04 - 2004/10  Kobe University大学院自然科学研究科JSPS Research fellow


  • 2000/04 - 2003/03  京都大学大学院理学研究科 博士後期課程
  • 1998/04 - 2000/03  大阪府立大学大学院工学研究科 博士前期課程
  • 1994/04 - 1998/03  Osaka Prefecture University  School of Engineering

Association Memberships

  • THE SOCIETY OF FLUORINE CHEMISTRY, JAPAN   Community of Bromine Application   The Society of Physical Organic Chemistry, Japan   The Japanese Association for Organic π-Electron Systems   THE SOCIETY OF POLYMER SCIENCE, JAPAN   American Chemical Society   THE SOCIETY OF SYNTHETIC ORGANIC CHEMISTRY, JAPAN   THE CHEMICAL SOCIETY OF JAPAN   

Published Papers

  • Yoshiki Sasaki, Masayoshi Takase, Shigeki Mori, Hidemitsu Uno
    Molecules 25 (11) 2486 - 2486 2020/05 [Peer-reviewed]
     Scientific journal 
    Hexapyrrolohexaazacoronene (HPHAC) is one of the N-containing polycyclic aromatic hydrocarbons in which six pyrroles are fused circularly around a benzene. Despite the recent development of HPHAC analogues, there is no report on direct introduction of functional groups into the HPHAC skeleton. This work reports the first example of nitration reaction of decaethylHPHAC. The structures of nitrodecaethylHPHAC including neutral and two oxidized species (radical cation and dication), intramolecular charge transfer (ICT) character, and global aromaticity of the dication are discussed.
  • Hidemitsu Uno, Kota Muramatsu, Shogo Hiraoka, Hiroyuki Tahara, Mako Hirose, Eidai Tamura, Tatsumi Shiraishi, John Mack, Nagao Kobayashi, Shigeki Mori, Tetsuo Okujima, Masayoshi Takase
    Chemistry – A European Journal 26 (25) 5701 - 5708 0947-6539 2020/05 [Peer-reviewed]
     Scientific journal
  • Kosuke Oki, Masayoshi Takase, Shigeki Mori, Hidemitsu Uno
    Journal of the American Chemical Society 141 (41) 16255 - 16259 0002-7863 2019/10 [Peer-reviewed]
     Scientific journal 
    Copyright © 2019 American Chemical Society. An antiaromatic cation of the expanded hexapyrrolohexaazacoronene (HPHAC) 1+ was synthesized by a Vilsmeier-type reaction of the partially unfused HPHAC 2. X-ray diffraction analysis revealed the formation of a seven-membered ring with a methyne linkage between the pyrrole moieties. Although 1+ is a monocation, upfield shifts of the peripheral ethyl protons were clearly observed in the 1H NMR spectra, indicating 24πantiaromaticity. Global antiaromaticity was also supported by nucleus-independent chemical shift and anisotropy of the induced current density calculations. Cation 1+ displayed two reversible oxidations and one irreversible reduction in the cyclic voltammetry measurements. Treatment of 1+ with NOSbF6 gave aromatic trication 13+ with 22π-electron conjugation.
  • Taniyuki Furuyama, Tetsuo Okujima, Kota Muramatsu, Yuichi Takahashi, Akihiro Mikami, Tomoteru Fukumura, Shigeki Mori, Takahiro Nakae, Masayoshi Takase, Hidemitsu Uno, Nagao Kobayashi
    European Journal of Organic Chemistry 2019 (20) 3224 - 3235 1434-193X 2019/06 [Peer-reviewed]
     Scientific journal 
    © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim A series of free-base and phosphorus(V) complexes of tetrabenzoporphyrin (TBP) and some phosphorus(V) porphyrins containing four or eight phenyl groups on the periphery have been synthesized and characterized by X-ray crystallography, electronic absorption, and magnetic circular dichroism (MCD) spectroscopy, together with quantum chemical calculations. All phosphorus TBP and meso-tetraphenyl porphyrin complexes adapted ruffled conformations due to the small P(V) ion, although the Zn(II)TBPs containing eight phenyl (Φ) groups at the so-called β and α positions showed planar and saddled structures in the solid state, due to, respectively, marginal or severe steric hindrance between the neighboring Φ groups. All P(V)TBPs showed the Soret and Q bands beyond 450 and 700 nm, respectively, which are some of the longest wavelengths exhibited by metallated TBPs reported to date. Of the eight Φ group-substituted P(V)TBPs, those substituted at α positions always showed absorption bands at longer wavelengths than those at β positions, which was reproduced by calculated absorption spectra. The Soret band positions of meso-tetraphenylated P(V) species without fused benzo-groups (ca. 430–440 nm) were also some of the longest among metalloporphyrins of this type.
  • Yoshiki Sasaki, Masayoshi Takase, Tetsuo Okujima, Shigeki Mori, Hidemitsu Uno
    Organic Letters 21 (6) 1900 - 1903 1523-7060 2019/03 [Peer-reviewed]
     Scientific journal 
    © 2019 American Chemical Society. Synthesis of an azacoronene, in which both pyrrole and azulene moieties are circularly fused, was achieved just in three steps. This new azacoronene exhibited multistep reversible oxidations under electrochemical and chemical conditions. Formation of an aromatic 22π-electron conjugation and a tropylium cation (6π-electron conjugation) in the dicationic state was revealed by the single-crystal X-ray crystallographic analysis as well as the nucleus-independent chemical shift (NICS) and anisotropy of the induced current density (ACID) calculations.
  • Hidemitsu Uno, Mako Hirose, Takayuki Honda, Shigeki Mori, Masayoshi Takase, Tetsuo Okujima
    Bulletin of the Chemical Society of Japan 92 (5) 1001 - 1007 0009-2673 2019/02 [Peer-reviewed]
     Scientific journal 
    © 2019 The Chemical Society of Japan Di(acenaphtho)-fused BODIPYs with four electron-withdrawing N,N-dimethylcarbamoyl groups were obtained by complexation of the corresponding dipyrrins, which were also proven to be a stable deep-red dye.
  • Hidemitsu Uno, Misaki Ishiwata, Kota Muramatsu, Masayoshi Takase, Shigeki Mori, Tetsuo Okujima
    Bulletin of the Chemical Society of Japan 92 (5) 973 - 981 0009-2673 2019/02 [Peer-reviewed]
     Scientific journal 
    © 2019 The Chemical Society of Japan. 1,3-Dihydrothieno[3,4-a]- and 1,3,8,10-tetrahydrodithieno-[3,4-a;3¤4¤-m]-HPHACs were prepared by the successive SNAr reactions of hexafluorobenzene with 1,3-dihydrothieno[3,4-c]-pyrrole and 3,4-dihexylpyrrole followed by Scholl oxidation. Oxidation of 1,3-dihydrothieno-fused HPHACs with excess amounts of iodine at room temperature quantitatively gave the corresponding dication bis(triiodide)s. Further dehydrogenative oxidation of the dicationic species with iodine giving a thieno-[3,4-a]HPHAC dication was achieved at a higher temperature by removing hydrogen iodide generated during the reaction. Neutral species of thieno[3,4-a]HPHAC could not be isolated.
  • Tetsuo Okujima, Kota Muramatsu, Shigeki Mori, Masayoshi Takase, Hidemitsu Uno
    Heterocycles 99 (2) 1434 - 1443 0385-5414 2019 [Peer-reviewed]
     Scientific journal 
    © 2019 The Japan Institute of Heterocyclic Chemistry. We have successfully synthesized 2,3-di(3-thienyl)benzo[b]porphyrin based on retro Diels-Alder reaction of bicyclo[2.2.2]octadiene(BCOD)-fused porphyrin and investigated its photoisomerization reaction.
  • Tetsuo Okujima, Hayato Inaba, Shigeki Mori, Masayoshi Takase, Hidemitsu Uno
    Journal of Porphyrins and Phthalocyanines 1088-4246 2019 [Peer-reviewed]
     Scientific journal 
    © 2019 World Scientific Publishing Company. A ring-contracted carbaporphyrin, azulitriphyrin(2.1.1), was synthesized via intramolecular McMurry coupling reaction. Absorption, NMR spectra and NICS calculations of protonated azulitriphyrin(2.1.1) revealed its Hückel aromatic character as a 14 porphyrinoid.
  • Akahane, T, Takase, M, Mazaki, Y, Nishinaga, T
    Heteroatom Chemistry 29 e21452  1042-7163 2018/11 [Peer-reviewed][Invited]
     Scientific journal
  • Kosuke Oki, Masayoshi Takase, Shigeki Mori, Akitoshi Shiotari, Yoshiaki Sugimoto, Keishi Ohara, Tetsuo Okujima, Hidemitsu Uno
    Journal of the American Chemical Society 140 (33) 10430 - 10434 0002-7863 2018/08 [Peer-reviewed]
     Scientific journal 
    Copyright © 2018 American Chemical Society. A core-expanded, pyrrole-fused azacoronene analogue containing two unusual N-doped heptagons was obtained from commercially available octafluoronaphthalene and 3,4-diethylpyrrole in two steps as a heteroatom-doped nonplanar nanographene. Full fusion with the formation of the tetraazadipleiadiene framework and the longitudinally twisted structure was unambiguously confirmed by single-crystal X-ray diffraction analysis. The edge-to-edge dihedral angle along the acene moiety was 63°. This electron-rich π-system showed four reversible oxidation peaks. Despite the nonplanar structure, the Hückel aromaticity owing to a peripheral π-conjugation in the dicationic state was concluded from the bond-length alternation and nucleus-independent chemical shift (NICS) and anisotropy of the induced current density (ACID) calculations.
  • Takashi Fujio, Tomohiro Miwata, Masayoshi Takase, Shunsuke Sueki, Kotohiro Nomura
    Journal of the Chinese Chemical Society 65 (3) 317 - 324 2192-6549 2018/03 [Peer-reviewed][Invited]
     International conference proceedings 
    Precise, efficient one-pot synthesis of star shaped (tri-, tetra-arm) π-conjugated systems has been achieved by olefin metathesis of 5-substituted-2-propenyl-thiophene or N-vinyl carbazole (arm segment) using a molybdenum-alkylidene reagent and subsequent Wittig-type cleavage with core segments containing aldehydes [tri(4-formylphenyl)amine, 2,4,6-tri(4-formyl-biphenyl)benzene, 1,4-dimethoxy-2,3,5,6-tetra(4-formylphenyl)-benzene, etc.] effects of the core and the arm have been clearly demonstrated.
  • Hidemitsu Uno, Takayuki Honda, Manami Kitatsuka, Shogo Hiraoka, Shigeki Mori, Masayoshi Takase, Tetsuo Okujima, Takahiro Nakae
    RSC Advances 8 (25) 14072 - 14083 2046-2069 2018 [Peer-reviewed]
     Scientific journal 
    © 2018 The Royal Society of Chemistry. Benzene-fused bis(acenaphthoBODIPY)s prepared by retro-Diels-Alder reaction of bicyclo[2.2.2]octadiene-fused precursors showed strong absorption bands in the near-infrared region and very weak absorptions in the visible region.
  • Hidemitsu Uno, Kazunari Tagawa, Shigeki Mori, Tetsuo Okujima, Masayoshi Takase, Takahiro Nakae
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 90 (12) 1375 - 1381 0009-2673 2017/12 Scientific journal 
    In this study, a benzene-fused bis(thiaporphyrin) was synthesized by the retro-Diels-Alder reaction of a bicyclo[2.2.2]octadiene (BCOD)-fused bis(thiaporphyrin) precursor. This precursor was prepared by the double [3+ 1] porphyrin synthesis of the BCOD-fused dipyrrole with thiatripyrrane. The ultraviolet-visible (UV-vis) spectrum of benzene-fused bis( thiaporphyrin) in dichloromethane was extremely different from that of the corresponding benzene-fused bis(porphyrin). In contrast, extremely similar spectra were obtained in the presence of trifluoroacetic acid. The similar electronic structures in the protonated states were supported by X-ray analysis and time-dependent density-functional theory (TD-DFT) calculations.
  • Shogo Hiraoka, Hiroyuki Tahara, Shigeki Mori, Tetsuo Okujima, Masayoshi Takase, Takahiro Nakae, Hidemitsu Uno
    TETRAHEDRON 73 (7) 957 - 963 0040-4020 2017/02 [Peer-reviewed]
     Scientific journal 
    Parikh-Doering oxidation of diethyl 9-hydroxy-2,6-dimethy1-4,8-dihydro-4,8-methanopyrrol[3,4-f]isoindole-1,7-dicarboxylate produced diethyl 9-oxo-2,6-dimethy1-4,8-dihydro-4,8-methanopyrrol[3,44] isoindole-1,7-dicarboxylate. This carbonyl derivative spontaneously underwent cheletropic extrusion of carbon monoxide, producing diethyl 2,6-dimethylpyrrol[3,4-f]isoindole-1,7-dicarboxylate, which showed 14 pi-electronic aromaticity on the whole five-six-five ring system. (C) 2017 Elsevier Ltd. All rights reserved.
  • Kazunari Tagawa, Shigeki Mori, Tetsuo Okujima, Masayoshi Takase, Hidemitsu Uno
    TETRAHEDRON 73 (6) 794 - 801 0040-4020 2017/02 [Peer-reviewed]
     Scientific journal 
    The protonation behavior of bicyclo[2.2.2]octadiene (BCOD)-fused thiaporphyrin and thiabenzoporphyrin was examined by titration with trifluoroacetic acid. Neutral, monorotonated, and diprotonated species of thiaporphyrins were easily detected by UV-vis spectral measurement. The first (K-1) and second (K-2) equilibrium constants were found to be K-1 = 520 and K-2 approximate to 7.1 for BCOD-fused thiaporphyrin and K-1 = 1.4 x 10(4) and K-2 approximate to 1.4 for thiabenzoporphyrin. The difference between K-1 and K-2 values of thiaporphyrins is larger than that observed for porphyrins (N-4-porphyrins). The main contributing conjugation pathways for thiaporphyrins in both protonated species were investigated by NICS and AICD quantum calculations using their atomic geometries obtained by X-ray structural analysis. The 18 pi-conjugation pathways of the neutral, monoprotonated, and diprotonated species thiaporphyrins were found to contain 18, 19, and 20 atoms, respectively. Results of H-1 NMR studies also support the major contributing pathways. (C) 2016 Elsevier Ltd. All rights reserved.
  • Kosuke Oki, Kazunari Tagawa, Shigeki Mori, Masayoshi Takase, Tetsuo Okujima, Hidemitsu Uno
    CHEMISTRY LETTERS 46 (2) 243 - 244 0366-7022 2017/02 [Peer-reviewed]
     Scientific journal 
    A cyclophane composed of diethanoanthracene (DEA)-fused dipyrrole and tetrafluorobenzene was synthesized by one-pot aromatic nucleophilic substitution (SNAr). Reflecting the fixed angle of DEA-fused dipyrrole, X-ray single-crystal structure analysis of the cyclophane revealed its rice-ball-shaped structure.
  • Kazunari Tagawa, Shigeki Mori, Masayoshi Takase, Tetsuo Okujima, Ichiro Hisaki, Hidemitsu Uno
    TETRAHEDRON LETTERS 57 (36) 4079 - 4081 0040-4039 2016/09 [Peer-reviewed]
     Scientific journal 
    In this study, hexagonal shape-persistent cyclophane with D-2h symmetry and rigid dihedral angles was obtained through the key SNAr reaction of perfluorobenzene moieties and dipyrroles. The X-ray analysis of the compound thus obtained revealed a hexagonal macrocyclic structure with D-2h symmetry due to the dihedral angles of 120 degrees and double 120 degrees for bicyclo[2.2.2]octadiene:fused dipyrrole and syn-diethanotetrahydroanthracene-fused dipyrrole, respectively. (C) 2016 Elsevier Ltd. All rights reserved.
  • Tetsuo Okujima, Hiroki Matsumoto, Shigeki Mori, Takahiro Nakae, Masayoshi Takase, Hidemitsu Uno
    TETRAHEDRON LETTERS 57 (29) 3160 - 3162 0040-4039 2016/07 [Peer-reviewed]
     Scientific journal 
    A complex of Cyclo[8]pyrrole with polyoxometalate, POM-to-Rings, was synthesized by anion exchange from cyclo[8]pyrrole sulfate. X-ray crystallographic study revealed the double-decker structure. (C) 2016 Elsevier Ltd. All rights reserved.
  • Tetsuo Okujima, Chie Ando, Saurabh Agrawal, Hiroki Matsumoto, Shigeki Mori, Keishi Ohara, Ichiro Hisaki, Takahiro Nakae, Masayoshi Takase, Hidemitsu Uno, Nagao Kobayashi
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 138 (24) 7540 - 7543 0002-7863 2016/06 [Peer-reviewed]
     Scientific journal 
    An acenaphthylene-fused cyclo[10]pyrrole 1b was selectively synthesized via an oxidative coupling reaction of the corresponding 2,2'-bipyrrole with the appropriate dianion template, croconate anion. The structure of 1b as the isolated largest cyclo[n]pyrrole was elucidated by X-ray crystallographic analysis. The absorption spectrum exhibited a markedly red-shifted, intensified L band at 1982 nm, which was interpreted by application of Michl's perimeter and Gouterman's 4-orbital models, supported by magnetic circular dichroism (MCD) data and theoretical calculations.
  • Masayoshi Takase
    Organic Redox Systems: Synthesis, Properties, and Applications 463 - 476 2015/12 [Peer-reviewed]
     In book 
    This chapter summarizes oligopyrroles and related compounds of linear and circular shapes from the viewpoints of redox-active functional materials. In the light of recent comprehensive reviews of porphyrin and related compounds including linear ones such as bile, only oligopyrroles possessing directly connected 2-2' bonds are highlighted. The investigation of oligomers with different chain lengths gives useful information for the molecular design that shows the desired optical and electronic properties and morphologies. Among them, linear oligomers are naturally the first choice for synthetic reasons. Based on the rich chemistry of oligopyrroles, the author and his coworkers reported the synthesis and physical properties of pyrrole-fused azacoronenes, namely, hexapyrrolohexaazacoronene (HPHAC). Pyrrole can stabilize its oxidation states by the nitrogen atom with strong electronegativity and also by releasing hydride. This feature of pyrrole with diversity in redox condition would be beneficial in designing novel π-electron materials.
  • Matthias Georg Schwab, Masayoshi Takase, Alexey Mavrinsky, Wojciech Pisula, Xinliang Feng, Jose A. Gamez, Walter Thiel, Kunal S. Mali, Steven de Feyter, Klaus Muellen
    CHEMISTRY-A EUROPEAN JOURNAL 21 (23) 8426 - 8434 0947-6539 2015/06 [Peer-reviewed]
     Scientific journal 
    A series of novel toroidal cyclo-2,9-tris-1,10-phenanthroline macrocycles with an unusual hexaaza cavity are reported. Nickel-mediated Yamamoto aryl-aryl coupling was found to be a versatile tool for the cyclotrimerization of functionalized 1,10-phenathroline precursors. Due to the now improved processability, both liquid-crystalline behavior in the bulk phase and two-dimensional self-assembly at the molecular level could be studied, for the first time, for a torand system. The macrocycles exhibited a strong affinity for the complexation of different metal cations, as evidenced by MALDI-TOF analysis and spectroscopic methods. Experimental results were correlated to an extensive computational study of the cyclo-2,9-tris-1,10-phenanthroline cavity and its binding mode for metal cations. Due to the combination of several interesting features, toroidal macrocycles may find future applications in the field of ion and charge transport through molecular channels, as well as for chemical sensing and molecular writing in surface-confined monolayers under STM conditions.
  • Hideyuki Shimizu, Jose D. Cojal Gonzalez, Masashi Hasegawa, Tohru Nishinaga, Tahmina Haque, Masayoshi Takase, Hiroyuki Otani, Juergen P. Rabe, Masahiko Iyoda
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 137 (11) 3877 - 3885 0002-7863 2015/03 [Peer-reviewed]
     Scientific journal 
    Two isomers of a multifunctional pi-expanded macrocyclic oligothiophene 8-mer, E,E-1 and Z,Z-1, were synthesized using a McMurry coupling of a dialdehyde composed of four 2,5-thienylene and three ethynylene units under high dilution conditions. On the other hand, cydo [8]-(2,5-thienylene-ethynylene) 2 was synthesized by intramolecular Sonogashira cydization of ethynyl bromide 5. From STM measurements, both E,E-1 and Z,Z-1 formed self-assembled monolayers at the solid liquid interface to produce porous networks, and from X-ray analyses of E,E-1 and 2, both compounds had a round shape with a honeycomb stacked structure. E,E-1 formed various fibrous polymorphs due to nanophase separation of the macrorings. E,E-1 and Z,Z-1 in solution exhibited photochromism upon irradiation and UV light, respectively, and this photoisomerization was confirmed by using STM. Furthermore, amorphous films of Z,Z-1 and E,E-1 showed photoisomerization, although single crystals, fibers, and square tubes of E,E-1 remained unchanged under similar conditions. E,E-1 with a 12.5-14.7 angstrom inner cavity incorporated fullerene C-60 in the cavity in solution and the solid state to produce a Saturn-like complex, whose structure was determined by X-ray analysis. 2 also formed a Saturn-like complex with C-60 in the solid state. These Saturn-like complexes are stabilized by van der Waals interactions between the sulfur atoms of 8-mer and C-60. The complexes exhibited charge-transfer interactions in the solid state. Like E,E-1, Saturn-like complex E,E-1 superset of C-60 formed small cube and fiber structures depending on the solvent used, whereas those of Saturn-like complex 2 superset of C-60 were limited due to the rigidity of the macroring of 2.
  • Masaki Tateno, Masayoshi Takase, Tohru Nishinaga
    CHEMISTRY OF MATERIALS 26 (12) 3804 - 3810 0897-4756 2014/06 [Peer-reviewed]
     Scientific journal 
    Gold-nanoparticles (AuNPs) protected by thiolates of methylthio end-capped terthiophene la and quaterthiophene 2a partially annelated with bicyclo[2.2.2]octene (BCO) unit(s) were designed and synthesized. AuNP covered with nonannelated terthiophene 3a was also synthesized for comparison. The formation of the AuNPs was confirmed by absorption spectra and transmission electron microscopy (TEM) measurements. The electric conductivities of AuNP-1a(-) and AuNP-3a(-) films were moderate (similar to 10(-3) S cm(-1)) due to conduction through core-to-core tunneling, whereas the conductivity of AuNP-2a(-) films was very low (<10(-6) S cm(-1)). The low conductivity of AuNP-2a(-) films would be due to a larger separation distance between the particles by two sterically demanding BCO units as suggested by the TEM analysis and DFT calculations. Importantly, after doping with iodine vapor, the enhancements in the conductivities of AuNP-1a(-) and AuNP-3a(-) were only 4- and 10-fold, respectively. In sharp contrast, the conductivity of AuNP-2a(-) after I-2-doping was increased by more than 10(4)-fold. The latter conductivity was comparable to the previously reported conductivities of AuNPs directly linked by oligothiophenes, and these results are consistent with the hypothesis that the electric conduction through g-dimers of oxidized oligothiophenes is as effective as through covalently linked oligothiophenes.
  • Manabu Kiguchi, Yuuta Takahashi, Shintaro Fujii, Masayoshi Takase, Tomoyuki Narita, Masahiko Iyoda, Masayo Horikawa, Yasuhisa Naitoh, Hisao Nakamura
    JOURNAL OF PHYSICAL CHEMISTRY C 118 (10) 5275 - 5283 1932-7447 2014/03 [Peer-reviewed]
     Scientific journal 
    We designed and synthesized a new quadrivial anchoring unit 4-TEB, to construct a stable single-molecule junction with gold electrodes, which should have equivalent conducting electron pathways between two electrodes. The conductances of single-molecule junctions comprising 4-TEB and its bidirectional counterpart 2-TEB were determined to be 2.7 x 10(-4)G(0) (2e(2)/h) and 5.0 X 10(-5)G(0), respectively, by using scanning tunneling microscope break junction (STM-BJ) techniques. The single 4-TEB molecule junction had higher stability and conductivity compared to those of the single 2-TEB molecule junction. Although the number of electron pathways from/to the electrode to/from the molecule was additive using the equivalent multianchoring the conductance of the single-molecule junction was not additive. From first-principles electronic transport calculations, the mechanism for the new quadrivial 4-TEB single-molecule junction involved an overlap resonance effect to the HOMO conducting orbital, giving rise to tunneling. Using fixed nanogap electrodes, we constructed stable molecular junctions of 4-TEB and observed symmetric peaks in the derivative of the conductance-voltage (G-V) curves, which were assigned to electron transport through the HOMO on the basis of theoretical calculations.
  • Takuya Kageyama, Shunsuke Uneme, Masayoshi Takase, Kotohiro Nomura, Tohru Nishinaga
    AUSTRALIAN JOURNAL OF CHEMISTRY 67 (5) 722 - 728 0004-9425 2014 [Peer-reviewed]
     Scientific journal 
    Benzo- and naphtho-annelated thiophene-pyrrole mixed octamers Bz8TP-C-m and Np8TP-C-m, comprising benzo- or naphthodithiophene and two dithienylpyrrole units, were synthesised. Density functional theory (DFT) calculations based on B3LYP/6-31G(d) with the broken symmetry method predicted that dications Bz8TP-C-1(2+) and Np8TP-C-1(2+) have stronger diradical character than previously investigated non-annelated thiophene-pyrrole mixed octamer 8TP-C-1(2+) (R-1 = R-2 = H). Compounds Bz8TP-C-8 and Np8TP-C-8 showed a one-step, two-electron oxidation process based on cyclic voltammetry analysis. Reaction with SbCl5 involved a two-electron oxidation. Bz8TP-C-8(2+) and Np8TP-C-8(2+) displayed similar absorption spectra to that of nonamer 9TP-C-12(2+) (R-1 = R-2 = H), rather than that of octamer 8TP-C-12(2+), indicating the stronger diradical characters of octamers Bz8TP-C-8(2+) and Np8TP-C-8(2+), as enhanced by benzo- and naphtho-annelation, and were comparable with that of 9TP-C-12(2+). Time-dependent-DFT calculations supported the conclusion obtained from the experimental results.
  • Tohru Nishinaga, Takuya Kageyama, Masahide Koizumi, Kyoko Ando, Masayoshi Takase, Masahiko Iyoda
    JOURNAL OF ORGANIC CHEMISTRY 78 (18) 9205 - 9213 0022-3263 2013/09 [Peer-reviewed]
     Scientific journal 
    A series of 2,5-di(2-thienyl)-N-methylpyrrole derivatives 1a-1d with methylthio end-capping groups and electrondonating substituents at the 3-position of the thiophene rings was synthesized, and the effects of the substituents on the structure, stability, and ir-dimerization ability of the radical cation investigated using UV vis NIR electron spin resonance spectra and density functional theory (DFT) calculations. Among the electron-donating methyl, methoxy, and methylthio substituents, the methoxy derivative lc gave the most stable radical cation, which persisted in dichloromethane at room temperature under nitrogen for several hours without any apparent decomposition. In addition, 1c(+) had the largest g-dimerization enthalpy among 1a(+) 1d(+). DFT calculations with the M06-2X method revealed that methyl and methylthio derivatives 1b(+) and 1d(+) as well as 1c(+) adopt a cis-cis conformation, in contrast to the trans-trans conformer of unsubstituted 1a(+), while the ir-dimers of all of these compounds were shown to have a cis cis conformation. On the basis of further detailed analyses, the preformed cis cis conformation and the weaker intramolecular and intermolecular steric repulsions were considered to explain why 1c(+) has the largest Ir-dimerization enthalpy.
  • Kazunari Aita, Takeshi Ohmae, Masayoshi Takase, Kotohiro Nomura, Hideaki Kimura, Tohru Nishinaga
    Organic Letters 15 (14) 3522 - 3525 1523-7060 2013/07 [Peer-reviewed]
     Scientific journal 
    The design and synthesis of a new planar cyclooctatetraene (COT) with protons directly connected to the COT ring was attained by monoannelation with dithieno[3,4-b:3′,4′-d]thiophene. The planar structure of the COT core was unambiguously confirmed by X-ray crystallography. The magnetic antiaromaticity of the COT core was found to be higher than that of the previously synthesized planar COTs with olefinic protons, according to the results of 1H NMR and absorption spectra as well as NICS calculations. © 2013 American Chemical Society.
  • Heejae Chung, Tomoyuki Narita, Jaesung Yang, Pyosang Kim, Masayoshi Takase, Masahiko Iyoda, Dongho Kim
    Chemistry - A European Journal 19 (29) 9699 - 9709 0947-6539 2013/07 [Peer-reviewed]
     Scientific journal 
    We have investigated the photophysical properties of star-shaped oligothiophenes with three terthiophene arms (meta to each other, S3) or six terthiophene arms (ortho-, meta-, and para-arranged, S6) connected to an ethynylbenzene core to elucidate the relationship between their molecular structure and electronic properties by using a combination of ensemble and single-molecule spectroscopic techniques. We postulate two different conformations for molecules S3 and S6 on the basis of the X-ray structure of hexakis(5-hexyl-2-thienlyethynyl)benzene and suggest the coexistence of these conformers by using spectroscopic methods. From the steady-state spectroscopic data of compound S6, we show that the exciton is delocalized over the core structure, but that the meta-linkage in compound S3 prevents the electronic communication between the arms. However, in single-molecule spectroscopic measurements, we observed that some molecules of compound S3 showed long fluorescence lifetimes (about 1.4 ns) in the fluorescence-intensity trajectories, which indicated that π electrons were delocalized along the meta linker. Based on these observations, we suggest that the delocalized exciton is intensely sensitive towards the dihedral angle between the core and the adjacent thiophene ring, as well as to the substituted position of the terthiophene arms. Our results highlight that the fluorescence lifetimes of compounds S3 and S6 are strongly correlated with the spatial location of their excitons, which is mainly affected by their conformation, that is, whether the innermost thiophene rings are facing each other or not. More interestingly, we observed that the difference between the degrees of ring-torsional flexibility of compounds S3 and S6 results in their sharply contrasting fluorescence properties, such as a change in fluorescence intensity as a function of temperature. Written in the stars: The electronic nature of star-shaped oligothiophenes can be controlled by increasing the number of branched arms (see figure), because these structural modifications lead to differences in the ring-torsional flexibility, which determines the degree of exciton delocalization throughout the core structure. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Masayoshi Takase, Ayumi Inabe, Yuki Sugawara, Wataru Fujita, Tohru Nishinaga, Kotohiro Nomura
    ORGANIC LETTERS 15 (13) 3202 - 3205 1523-7060 2013/07 [Peer-reviewed]
     Scientific journal 
    The expeditious synthesis of donor-acceptor segregated paracyclophanes has been achieved by a selective SNAr reaction of hexafluorobenzene with o-dipyrrolylbenzenes and subsequent cyclodehydrogenation. An orthogonally arranged D-A segregated structure was confirmed by X-ray crystallography. The combined results of DFT calculations and absorption spectra revealed the charge transfer (CT) nature from the naphthobipyrrole (donor) to the stacked fluoroarene moiety (acceptor).
  • Masayoshi Takase, Tomoyuld Narita, Wataru Fujita, Motoko S. Asano, Tohru Nishinaga, Hiroaki Benten, Kenji Yoza, Klaus Muellen
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 135 (21) 8031 - 8040 0002-7863 2013/05 [Peer-reviewed]
     Scientific journal 
    A novel pyrrole-fused azacoronene family was synthesized via oxidative cyclodehydrogenation of the corresponding hexaarylbenzenes as the key step, and the crystal structures of tetraazacoronene 3b and triazacoronene 4a were elucidated. The photophysical properties for neutral compounds 1-4 were investigated using steady-state UV-vis absorption/emission spectroscopy and time resolved spectroscopy (emission spectra and lifetime measurements) at both room temperature and 77 K. The observation of both fluorescence and phosphorescence allowed us to estimate the small S-1-T-1 energy gap (Delta ES-T) to be 0.35 eV (la), 0.26 eV (2a), and 0.36 eV (4a). Similar to the case of previously reported hexapyrrolohexaazacoronene 1 (HPHAC), electrochemical oxidation revealed up to four reversible oxidation processes for all of the new compounds. The charge and spin delocalization properties of the series of azacoronene pi-systems were examined using UV-vis-NIR absorption, ESR, and NMR spectroscopies for the chemically generated radical cations and dications. Combined with the theoretical calculations, the experimental results clearly demonstrated that the replacement of pyrrole rings with dialkoxybenzene plays a critical role in the electronic communication, where resonance structures significantly contribute to the thermodynamic stability of the cationic charges/spins and determine the spin multiplicities For HPHAC 1 and pentaazacoronene 2, the overall aromaticity predicted for dosed shell dications 1(2+) and 2(2+) was primarily based on the theoretical calculations, and the open shell singlet biradical or triplet character was anticipated for tetraazacoronene 3(2+) and triazacoronene 4(2+) with the aid of theoretical calculations These polycyclic aromatic hydrocarbons (PAHs) represent the first series of nitrogen containing PAHs that can be multiply oxidized.
  • Masaki Tateno, Masayoshi Takase, Masahiko Iyoda, Koichi Komatsu, Tohru Nishinaga
    CHEMISTRY-A EUROPEAN JOURNAL 19 (17) 5457 - 5467 0947-6539 2013/04 [Peer-reviewed]
     Scientific journal 
    A Two series of oligothiophenes 2(nT) (n=4,5), annelated with bicyclo[2.2.2]octene (BCO) units at both ends, and quaterthiophenes 3ac, annelated with various numbers of BCO units at different positions, were newly synthesized to investigate the driving forces of -dimerization and the structureproperty relationships of the -dimers of oligothiophene radical cations. Their radical-cation salts were prepared through chemical one-electron oxidation by using nitrosonium hexafluoroantimonate. From variable-temperature electron spin resonance and electronic absorption measurements, the -dimerization capability was found to vary among the members of the 2(nT)+.SbF6 series and 3+.SbF6 series of compounds. To examine these results, density functional theory (DFT) calculations at the M06-2X/6-31G(d) level were conducted for the -dimers. This level of theory was found to successfully reproduce the previously reported X-ray structure of (2(3T))22+ having a bent -dimer structure with ciscis conformations. The absorption bands obtained by time-dependent DFT calculations for the -dimers were in reasonable agreement with the experimental spectra. The attractive and repulsive forces for the -dimerization were divided into four factors: 1)SOMOSOMO interactions, 2)van der Waals forces, 3)solvation, and 4)Coulomb repulsion, and the effects of each factor on the structural differences and chain-length dependence are discussed in detail.
  • Tohru Nishinaga, Takeshi Ohmae, Kazunari Aita, Masayoshi Takase, Masahiko Iyoda, Tatsuya Arai, Yoshihito Kunugi
    CHEMICAL COMMUNICATIONS 49 (47) 5354 - 5356 1359-7345 2013 [Peer-reviewed]
     Scientific journal 
    Tetra[2,3-thienylene] planarised by sulphur bridges and radially pi-extended with (triisopropylsilyl)ethynyl groups had a narrow HOMO-LUMO gap due to the antiaromatic cyclooctatetraene core, and its single crystal FET device exhibited ambipolar characteristics with hole and electron mobilities of up to 0.40 and 0.18 cm(2) V-1 s(-1), respectively.
  • Lukas F. Doessel, Valentin Kamm, Ian A. Howard, Frederic Laquai, Wojciech Pisula, Xinliang Feng, Chen Li, Masayoshi Takase, Tibor Kudernac, Steven De Feyter, Klaus Muellen
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 134 (13) 5876 - 5886 0002-7863 2012/04 [Peer-reviewed]
     Scientific journal 
    We report the synthesis and photophysical characterization of a series of hexa-peri-hexabenzocoronene (HBC)/perylenetetracarboxy diimide (PDI) dyads that are covalently linked with a rigid bridge. Both the ratio of the vs. two components and the conjugation of the bridging element are systematically modified to study the influence on self-assembly and energy and electron transfer between electron donor HBC and acceptor PDI. STM and 2D-WAXS experiments reveal that both in solution and in bulk solid state the dyads assemble into well-ordered two-dimensional supramolecular structures with controllable mutual orientations and distances between donor and acceptor at a nanoscopic scale. Depending on the symmetry of the dyads, either columns with nanosegregated stacks of HBC and PDI or interdigitating networks with alternating HBC and PDI moieties are observed. UV-vis, photoluminescence, transient photoluminescence, and transient absorption spectroscopy confirm that after photoexcitation of the donor HBC a photoinduced electron transfer between HBC and PDI can only compete with the dominant Forster resonance energy transfer, if facilitated by an intimate stacking of HBC and PDI with sufficient orbital overlap. However, while the alternating stacks allow efficient electron transfer, only the nanosegregated stacks provide charge transport channels in bulk state that are a prerequisite for application as active components in thin film electronic devices. These results have important implications for the further design of functional donor acceptor dyads, being promising materials for organic bulk heterojunction solar cells and field-effect transistors.
  • Masayoshi Takase, Naofumi Yoshida, Tomoyuki Narita, Takashi Fujio, Tohru Nishinaga, Masahiko Iyoda
    RSC ADVANCES 2 (8) 3221 - 3224 2046-2069 2012 [Peer-reviewed]
     Scientific journal 
    Sterically congested pyrrole-fused tetrathiafulvalene (TTF) decamer 4 was designed and synthesized via the SNAr reaction of decafluorobiphenyl with the corresponding pyrrolyl sodium salt, which formed amorphous spin-coated films showing good conductivity of up to 4.4 S cm(-1) after iodine doping as the result of multi-dimensional pi-pi stacking between the TTF units.
  • Yoshimi Hanai, M. Jalilur Rahman, Jun Yamakawa, Masayoshi Takase, Tohru Nishinaga, Masashi Hasegawa, Kenji Kamada, Masahiko Iyoda
    CHEMISTRY-AN ASIAN JOURNAL 6 (11) 2940 - 2945 1861-4728 2011/11 [Peer-reviewed]
     Scientific journal 
    Conjugated benzenoid aromatics with large inner cavities and alkyl side chains self-associate to produce dimers in solution and fibrous materials in the solid state. The self-association is enthalpically and entropically driven. The compound forms a 1:3 charge-transfer (CT) complex with 2,4,7-trinitrofluorenone (TNF) with a microball structure, where a nano-sized branched structure forms first at the growth points, followed by production of the microball with a dendritic interior. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Masahiko Iyoda, Yoshiyuki Kuwatani, Tohru Nishinaga, Masayoshi Takase, Tomohiko Nishiuchi
    Fragments of Fullerenes and Carbon Nanotubes: Designed Synthesis, Unusual Reactions, and Coordination Chemistry 311 - 342 2011/10 In book
  • Masayoshi Takase, Naofumi Yoshida, Tohru Nishinaga, Masahiko Iyoda
    ORGANIC LETTERS 13 (15) 3896 - 3899 1523-7060 2011/08 [Peer-reviewed]
     Scientific journal 
    A series of star-shaped pyrrole-fused tetrathiafulvalene (TTF) oligomers 1-3 was synthesized via an S(N)Ar reaction of fluorinated benzenes with the pyrrolyl sodium salts. Electrochemical and chemical oxidations of 1-3 revealed that a radical cation moiety on each TTF unit was successfully accumulated in all oligomers. Self-assembled structures of neutral and oxidized species were characterized by SEM and XRD, and their conductive properties of the Iodine-doped 1-3 as well as an intermolecular mixed-valence ion radical salt were investigated.
  • Chuanwen Lin, Takanori Endo, Masayoshi Takase, Masahiko Iyoda, Tohru Nishinaga
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133 (29) 11339 - 11350 0002-7863 2011/07 [Peer-reviewed]
     Scientific journal 
    A series of 3,4-propylenedioxythiophene (ProDOT) oligomers (nP(Hex)) with dihexyl side chains and methylthio end-capping units was synthesized as a model of poly(3,4-alkylenedioxythiophene)s. The slope of the linear relationship between the energy of the absorption maxima of nP(Hex) in the neutral states and the reciprocal of the number of monomer units (1/n) was found to be comparable to that of 3,4-ethylenedioxythiophene (EDOT) oligomers, suggesting that both the ProDOT and the EDOT oligomers have a similar effective conjugation. In cyclic voltammetry measurements, both the first and second oxidation waves and the third and fourth waves were shown to merge into one peak with increasing chain length. The stepwise chemical oxidations of nP(Hex) with SbCl5 in CH2Cl2 at room temperature gave their stable cationic species in various oxidation states, and it was found that only the radical cations (polarons) have an obvious absorption band in the visible region. Interestingly, when the absorption spectra of tetramer radical cation 4P(Hex)(+center dot). were measured at low temperatures, reversible disproportionation into dication 4P(Hex)(2+) and neutral species 4P(Hex) was observed in addition to pi-dimer formation. Furthermore, the radical cations of the longer oligomers showed only the disproportionation reaction. From the comparisons of the results of experiments and the theoretical calculations of the dications, 6P(Hex)(2+) was found to have a closed-shell nature, and only a weak singlet biradical character appeared even in longer oligomers 10P(Hex)(2+) and 12P(Hex)(2+). Overall, the electron-donating dioxy substituents are considered to stabilize high p-doping levels with closed-shell dication (bipolaron) structures in poly(3,4-alkylenedioxythiophene)s, which enables the transparency properties of the polymers.
  • Masahiko Iyoda, Pochi Huang, Tomohiko Nishiuchi, Masayoshi Takase, Tohru Nishinaga
    HETEROCYCLES 82 (2) 1143 - + 0385-5414 2011/03 [Peer-reviewed]
     Scientific journal 
    The reaction of diformyldithienylacetylene 4 with a McMurry reagent prepared from TiCl(4), Zn, and pyridine in THF afforded 24 pi-dimer 1b (15%), 36 pi-trimer 2b (13%), and 48 pi-tetramer 3b (6%). From X-ray analysis, 1b adopts a twisted conformation, although the (1)H NMR spectrum of 1b shows a symmetrical structure owing to a rapid conformational change in solution. Absorption and emission spectra, redox properties, and electric conductivities of 1b-3b were measured in order to study the structure-property relationship of these macrocyclic systems.
  • Tohru Nishinaga, Toshihiko Miyata, Masaki Tateno, Masahide Koizumi, Masayoshi Takase, Masahiko Iyoda, Norihito Kobayashi, Yoshihito Kunugi
    JOURNAL OF MATERIALS CHEMISTRY 21 (38) 14959 - 14966 0959-9428 2011 [Peer-reviewed]
     Scientific journal 
    alpha-Linked thiophene-pyrrole mixed hexamers 3a-5a end-capped with two phenyl, two pentafluorophenyl and both phenyl and pentafluorophenyl units were newly synthesized, and their structural, electronic, optical and FET properties were investigated. Structural analyses by means of X-ray crystallography and theoretical calculations showed that the pi-system of the oligomer chains is twisted due to the steric repulsion between the hexyl group of the pyrrole unit and the adjacent thiophene moiety. From comparison of the absorption maxima and redox potentials, end-capping with phenyl and pentafluorophenyl units did not affect the HOMO-LUMO gap for the thiophene-pyrrole hexamer, and the multiple fluorine substituents slightly decreased both HOMO and LUMO levels by the inductive effects of the electronegative fluorine atoms. Although the diphenyl derivative 3a with a herringbone-type packing structure did not serve as an active layer for FET devices, a unique crystal-to-crystal phase transition with a color change from yellow to red was observed upon heating. In contrast to the herringbone-type packing structure of 3a, the unsymmetrical phenyl-pentafluorophenyl derivative 5a showed a partially pi-stacked structure, most likely due to dipole-dipole interactions. The pi-stacked structure of 5a caused a good hole mobility of 4.1 x 10(-2) cm(2) V-1 s(-1) in a single crystal FET device.
  • Tohru Nishinaga, Masaki Tateno, Mika Fujii, Wataru Fujita, Masayoshi Takase, Masahiko Iyoda
    ORGANIC LETTERS 12 (23) 5374 - 5377 1523-7060 2010/12 [Peer-reviewed]
     Scientific journal 
    Combined DFT calculations and UV-vis-NIR, ESR, and SQUID measurements revealed that the ground-state electronic structure of a linear pi-conjugated oligomer dication composed of two pyrrole and six or seven thiophene rings and methylthio end-capping units is dominated by a singlet biradical character.
  • Masayoshi Takase, Masahiko Iyoda
    Conjugated Polymer Synthesis: Methods and Reactions 165 - 194 2010/11 [Peer-reviewed]
     In book
  • Yohei Honna, Eigo Isomura, Hideo Enozawa, Masashi Hasegawa, Masayoshi Takase, Tohru Nishinaga, Masahiko Iyoda
    TETRAHEDRON LETTERS 51 (4) 679 - 682 0040-4039 2010/01 [Peer-reviewed]
     Scientific journal 
    The FeCl3-mediated homo-coupling of 4,5-bis(alkylthio)-4'-tetrathiafulvalenylmagnesium bromide 5 produced the corresponding bitetrathiafulvalene derivatives 2a-d in moderate yields (25-51%). Bitetrathiafulvalenes 2c and 2d having long alkylthio chains formed nanostructures and showed bulk electric conductivities (sigma(rt) = 2.6 - 8.0 x 10(-5) S cm(-1)) in the neutral state owing to the fastener effect. Interestingly, the nanofiber of tetrakis(dodecylthio)bitetrathiafulvalene 2d exhibited a p-type semiconductivity as detected by AFM. (C) 2009 Elsevier Ltd. All rights reserved.
  • Tomoyuki Narita, Masayoshi Takase, Tohru Nishinaga, Masahiko Iyoda, Kenji Kamada, Koji Ohta
    CHEMISTRY-A EUROPEAN JOURNAL 16 (40) 12108 - 12113 0947-6539 2010 [Peer-reviewed]
     Scientific journal 
    Shining star: Star-shaped hexakis(oligothienylethynyl)benzene with C 6 symmetry shows solvatochromic fluorescence with a marked redshift in emission. Furthermore, the star-shaped molecule shows a fairly large two-photon absorption property. Interestingly, the molecule forms fluorescent fibrous materials from hexane, DMF, and isopropyl alcohol owing to its disc-like structure (see graphic). © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Dongqing Wu, Xinliang Feng, Masayoshi Takase, Monika C. Haberecht, Klaus Muellen
    TETRAHEDRON 64 (50) 11379 - 11386 0040-4020 2008/12 [Peer-reviewed]
     Scientific journal 
    A novel synthetic method toward nitrogen containing positively charged dibenzo[jk,mn]naptho[2,1,8-fgh]thebenidinium (DBNT, 1) salts was developed. In this method, the undehydrogenated precursor of DBNT, 14-phenyl-14-dibenzo[aj]acridinium salt (6), was produced directly from the reaction between 14-phenyl-14-dibenzo[aj]xanthenylium (2) and annine/aniline in reasonable yield. Various DBNT salts with different alkyl and alkylphenyl chains were synthesized in this two-step method. The self-assembly behavior of two alkylated DBNT salts, 1c and If, Was Studied in this work. Due to the different substituents and counterions, Compound 1c formed nanoscale wirelike fibers, and helical aggregates were obtained from 1f, in their methanolic solutions. (C) 2008 Elsevier Ltd. All rights reserved.
  • Xinliang Feng, Miaoyin Liu, Wojciech Pisula, Masayoshi Takase, Jiaoli Li, Klaus Muellen
    ADVANCED MATERIALS 20 (14) 2684 - + 0935-9648 2008/07 [Peer-reviewed]
     Scientific journal 
    Two novel triangle-shaped discotic graphenes with swallow-like alkyl tails are synthesized; these discotic graphenes allow facile purification, control over thermotropic properties, and solution fabrication into efficient photovoltaic devices. The unique molecular design results in an extremely broad liquid-crystalline range and the ability to self-heal at low processing temperatures, which improves the performance of photovoltaic cells.
  • Xinliang Feng, Wojciech Pisula, Masayoshi Takase, Xi Dou, Volker Enkelmann, Manfred Wagner, Ning Ding, Klaus Muellen
    CHEMISTRY OF MATERIALS 20 (9) 2872 - 2874 0897-4756 2008/05 [Peer-reviewed]
     Scientific journal 
    A study was conducted to analyze the synthesis, helical organization, and fibrous formation of C 3 symmetric Methoxy-substituted discotic hexa-peri-hexabenzocoronene (HBC). HBCs were synthesized using the oxidative cyclodehydrogenations of proper hexaphenyl-benzene precursors. NMR spectroscopy was used to analyze the property of HBCs toward self-assembly in solution. The self-assembly led to fibrous nanostructures with several hundred micrometers in length upon drop-casting. Differential scanning calorimetry (DSC) was used to observe thermotropic properties of HBCs. The UV-vis and photoluminescence spectra was used to analyzed internal structure of HBCs for observing fibrous structures. Results show that HBC with three alternative dodecyl1 and methoxy substitutions was synthesized using the Scholl reaction.
  • Xinliang Feng, Wojciech Pisula, Linjie Zhi, Masayoshi Takase, Klaus Muellen
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 47 (9) 1703 - 1706 1433-7851 2008 [Peer-reviewed]
     Scientific journal 
    Everysecond counts: Enhanced control over the self-organization of discotic compounds has been obtained by introducing alternating arrays of apolar (alkyl) and polar (ester) substitutents on to C 3 -symmetric hexa-peri-hexabenzocoronenes. The local dipole moments and the nanophase separation between the polar and apolar sites significantly influence the self-assembly in solution and in the solid state (see schematic representation). (Figure Presented). © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.
  • Masayoshi Takase, Volker Enkelmann, Daniel Sebastiani, Martin Baumgarten, Klaue Muellen
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 46 (29) 5524 - 5527 1433-7851 2007 [Peer-reviewed]
     Scientific journal 
    (Figure Presented) The heteroatom-stabilized annularly fused hexapyrrolohexaazacoronene shown (N blue, F green) was synthesized and isolated as a representation of a new class of nitrogen-containing molecules with extended π systems. The reversible redox behavior, a consequence of the interior N atoms, hints at potential applications in organic electronics. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.
  • T Takeuchi, Y Minato, M Takase, H Shinmori
    TETRAHEDRON LETTERS 46 (52) 9025 - 9027 0040-4039 2005/12 [Peer-reviewed]
     Scientific journal 
    Molecular recognition materials bearing halogen bonding-based binding sites were synthesized by a non-covalent imprinting technique using a 2,3,5,6-tetrafluoro-4-iodostyrene (TFIS) as the functional monomer. The binding sites were generated by co-polymerizing TFIS, styrene and divinylbenzene in the presence of the template molecule (4-dimethylaminopyridine-DMAP). The imprinted polymer preferentially adsorbed aminopyridine derivatives, suggesting that halogen bonding may play a role in the selective recognition of analytes by the synthesized synthetic receptor. (c) 2005 Elsevier Ltd. All rights reserved.
  • M Inouye, R Ikeda, M Takase, T Tsuri, J Chiba
    PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA 102 (33) 11606 - 11610 0027-8424 2005/08 [Peer-reviewed]
     Scientific journal 
    Establishing a reliable genotyping protocol is a critical matter in postsequence genetics. In this article, we describe a highly sensitive electrochemical detection of complementary DNAs (up to 43-mer) based on hole transport with molecular-scale, "wire-like" DNA probes. The presence of a single-base mismatch in the DNA duplexes caused a dramatic decrease in the electrochemical response. We applied this method to detect all of the possible transition and transversion SNPs and achieved "on-off"-type discrimination of fully complementary DNAs from their SNPs. Furthermore, naturally occurring polymorphisms, "hot spots" from the p53 gene, could clearly be distinguished from wild type by using our methodology.
  • H Abe, M Takase, Y Doi, S Matsumoto, M Furusyo, M Inouye
    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (14) 2931 - 2940 1434-193X 2005/07 [Peer-reviewed]
     Scientific journal 
    A triple hydrogen-bonding module based on 6-alkynyl-2-amino-3H-pyrimidin-4-one was developed such as for self-dimerization and for nucleobase recognition processes. The strength of the module for the self -dimerization was determined by NMR and fluorimetric analyses in chloroform (Delta G(298) = -22 to -23 kJ/mol). DFT calculations and X-ray structure analysis showed that the self -dimerization consists of the three-point hydrogen-bonding including two kinds of tautomers of the module in an ADD-DAA mode. Selective recognition of the module for a cytidine derivative was also observed, and the free energy change for the complexation (Delta G(298) = -31 kJ/mol) is one of the highest values among triple hydrogen-bonded complexes so far reported. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
  • M Takase, A Nakajima, T Takeuchi
    TETRAHEDRON LETTERS 46 (10) 1739 - 1742 0040-4039 2005/03 [Peer-reviewed]
     Scientific journal 
    An extended hexagonal molecule that has high symmetry and rigidity was designed and synthesized by a cobalt-catalyzed cyclotrimerization reaction. The ligand possesses six benzoic acids at its periphery, which were connected to a central hexakis(2,5-dodesyloxyphenyl)hexaphenylbenzene core with a maximum intramolecular carboxyl group distance of approximately 3.5 nm. (C) 2005 Elsevier Ltd. All rights reserved.
  • T Takeuchi, S Ugata, S Masuda, J Matsui, M Takase
    ORGANIC & BIOMOLECULAR CHEMISTRY 2 (18) 2563 - 2566 1477-0520 2004 [Peer-reviewed]
     Scientific journal 
    Atrazine imprinted synthetic polymers were prepared using a combination of methacrylic acid and 2-sulfoethyl methacrylate that bound and converted atrazine and other 6-chlorotriazine herbicides to less toxic compounds. A chloride at the 6-position of the triazines was converted to a methoxy group by the polymer in a methanol-containing solvent, where the imprinting effects enhanced the catalytic activity. Competitive inhibition of the atrazine methanolysis was observed in the presence of a structurally related binder, ametryn, suggesting that the catalytic reaction proceeded in the binding sites generated by the molecular imprinting process.
  • HS Cho, H Rhee, JK Song, CK Min, M Takase, N Aratani, S Cho, A Osuka, T Joo, D Kim
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 125 (19) 5849 - 5860 0002-7863 2003/05 [Peer-reviewed]
     Scientific journal 
    Femtosecond fluorescence anisotropy measurements for a variety of cyclic porphyrin arrays such as Zn(II)porphyrin m-trimer and hexamer are reported along with o-dimer and monomer as reference molecules. In the porphyrin arrays, a pair of porphyrin moieties are joined together via triphenyl linkage to ensure cyclic and rigid structures. Anisotropy decay times of the porphyrin arrays can be well described by the Forster incoherent excitation hopping process between the porphyrin units. Exciton coupling strengths of 74 and 264 cm(-1) for the m-trimer and hexamer estimated from the observed excitation energy hopping rates are close to those of B800 and B850, respectively, in the LH2 bacterial light-harvesting antenna. Thus, these cyclic porphyrin array systems have proven to be useful in understanding energy migration processes in a relatively weak interaction regime in light of the similarity in overall structures and constituent chromophores to natural light-harvesting arrays.
  • M Takase, T Morikawa, H Abe, M Inouye
    ORGANIC LETTERS 5 (5) 625 - 628 1523-7060 2003/03 [Peer-reviewed]
     Scientific journal 
    [GRAPHICS] The reaction of 3,5-di-O-benzyl-2-deoxy-D-ribofuranose with various alkynyllithium reagents afforded diastereomeric mixtures of the corresponding ring-opened alkynyldiols. The resulting diastereomeric mixtures were successively treated with CO2(CO)(8), a catalytic amount of TfOH, Et3N, and iodine in one pot to give alkynyl C-3,5-di-O-benzyl-2-deoxy-beta-D-ribofuranosides with high beta-selectivities. The cobalt-mediated cyclization (intramolecular Nicholas reaction) is reversible; thus, thermodynamically more stable beta-anomers were obtained preferentially. The alkynyl C-deoxyribofuranosides were converted to a variety of C-deoxyribofuranoside derivatives.
  • M Takase, M Inouye
    JOURNAL OF ORGANIC CHEMISTRY 68 (3) 1134 - 1137 0022-3263 2003/02 [Peer-reviewed]
     Scientific journal 
    Synthesis and binding affinity of rationally designed artificial ditopic nucleobase receptors are reported. The ditopic receptors were designed to recognize thymine-thymine dinucleotides by their two hydrogen-bonding moieties, which are connected to conformationally well-defined linkages such as ferrocene and biphenylene. The ditopic receptors exhibited a remarkably strong binding affinity for lipophilic TpT analogue in CDCl3/DMSO-d(6) (85:15, v/v). The binding affinity of the ditopic receptors for the dinucleotide was so high that even native TpT was extracted by them into CDCl3. Detailed comparisons for the recognition abilities of the ditopic receptors were also conducted.
  • M Takase, R Ismael, R Murakami, M Ikeda, D Kim, H Shinmori, H Furuta, A Osuka
    TETRAHEDRON LETTERS 43 (29) 5157 - 5159 0040-4039 2002/07 [Peer-reviewed]
     Scientific journal 
    Palladium- and cobalt-catalyzed trimerization of diphenylethynyl-bridged diporphyrin gave benzene-centered cyclic porphyrin hexamers. (C) 2002 Elsevier Science Ltd. All rights reserved.
  • M Inouye, M Takase
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 40 (9) 1746 - 1748 1433-7851 2001 [Peer-reviewed]
     Scientific journal 
    The multipoint hydrogen-bonded complex 1 (R = alkanoyl) is readily formed between a ferrocene-modified artificial receptor and a dinucleotide. This principle can be used effectively in highly selective, large-scale separations of dinucleotides from mixtures of mono- and oligonucleotides. The process is economically viable and environmentally friendly.
  • M Takase, M Inouye
    CHEMICAL COMMUNICATIONS (23) 2432 - 2433 1359-7345 2001 [Peer-reviewed]
     Scientific journal 
    A ferrocene-linked bis(spiropyridopyran) was designed and synthesized, that recognized guanine-guanine dinucleoside derivatives via complementary hydrogen bonds in CH2Cl2, resulting in the isomerization of the colorless spiropyridopyran as self-indicating receptors.
  • M Takase, M Inouye
    MOLECULAR CRYSTALS AND LIQUID CRYSTALS 344 313 - 318 1058-725X 2000 Scientific journal 
    A novel ferrocene-modified bis(spirobenzopyran) was designed and synthesized. The spirobenzopyran possesses two photochromic moieties, which were tethered to two cyclopenta-dienyl rings of ferrocene via ethynediyl spacers. Photochromic properties of the spirobenzopyran were investigated in the absence and presence of various metal cations.

Books etc

  • Creation of Nitrogen-Embedded Nanographene Based on Pyrrole
    Masayoshi Takase (Contributor, 月刊ファインケミカル2010年1月号「ナノグラフェンの合成と用途開発」)
    シーエムシー出版 2020/01
  • "Oligopyrroles and Related Compounds" in Organic Redox Systems – Synthesis, Properties, and Applications (Ed. Nishinaga. T.)
    Masayoshi Takase (Single work)
    Wiley-VCH Verlag GmbH & Co. KGaA 2015/12 9781118858745 14 463-476
  • "Conjugated Molecular Belts Based on 3-D Benzannulene Systems" in Fragments of Fullerenes and Carbon Nanotubes: Designed Synthesis, Unusual Reactions, and Coordination Chemistry (Eds. Petrukhina, M. A. and Scott, L. T.)
    Iyoda, M, Kuwatani, Y, Nishinaga, T, Takase, M, Nishiuchi, T 
    John Wiley & Sons, Inc. NJ 2011/11 9780470569085 440 311-342
  • "Fully Conjugated Nano-sized Macrocycles: Syntheses and Versatile Properties" in Conjugated Polymer Synthesis - Methods and Reactions (Ed. Chujo, Y.)
    Takase, M, Iyoda, M 
    2010/11 9783527632664 165-194
  • "Supramolecular Structures and Nanoassemblies of Oligothiophenes and Tetrathiafulvalenes" in Top. Heterocycl. Chem.
    Iyoda, M, Nishinaga, T, Takase, M 
    Springer 2009/03 103-118
  • "Molecular Recognition of DNA-Relevant Molecules by Conformationally Well-Defined Multi-Topic Artificial Receptors" in Recent Res. Devel. Organic. Chem.
    Inouye, M, Takase, M 
    Transworld Research Network 2003 141-153

Conference Activities & Talks

  • 酸化還元特性を有するPAHの合成と機能  [Invited]
    第3回集合有機分子機能研究会  2019/08  岡山
  • Masayoshi Takase, Kosuke Oki, Shigeki Mori, Hidemitsu Uno
    The 18th International Symposium on Novel Aromatic Compounds (ISNA-18)  2019/07  Sapporo
  • 高瀬雅祥
    愛媛大学 リサーチユニット研究会:機能性固体材料の最前線  2019/03  松山
  • Masayoshi Takase, Kosuke Oki, Yoshiki Sasaki, Shigeki Mori, Tetsuo Okujima, Hidemitsu Uno
    The 3rd International Symposium on the Synthesis and Application of Curved Organic π-Molecules & Materials (CURO-Pi III)  2018/09  Oxford, UK
  • Masayoshi Takase
    The 233rd Electrochemical Society Meeting (ECS Meeting)  2018/05  Seattle, USA
  • Masayoshi Takase, Kosuke Oki, Ryosuke Ohmasa, Shigeki Mori, Tetsuo Okujima, Hidemitsu Uno
    第40回フッ素化学討論会  2017/11  鳥取
  • ピロールを用いた拡張π電子系化合物の合成と機能  [Invited]
    第1回集合有機分子機能研究会  2017/07  小樽
  • ピロールを用いた芳香族求核置換反応を鍵反応とするアザコロネン類の合成と物性  [Not invited]
    高瀬雅祥, 沖 光脩, 佐々木良城, 藤原和輝, 小川竜摩, 森 重樹, 奥島鉄雄, 宇野英満
    第111回有機合成シンポジウム  2017/06  岡山
  • Synthesis and Properties of Pyrrole-fused Azacoronene and Its Derivatoves  [Invited]
    Masayoshi Takase
    6th Georgian Bay International Conference on Bioinorganic Chemistry (CanBIC-6)  2017/05
  • ピロールを含む新しいπ電子共役系化合物の開発  [Invited]
    第32回若手化学者のための化学道場  2016/08  松山
  • Pyrrole-Based Polycyclic Pi-Electron Systems with Various Redox States  [Invited]
    Masayoshi Takase
    The 229th Electrochemical Society Meeting (ECS Meeting)  2016/06
  • ピロールを基本骨格とするπ電子系化合物の創成  [Invited]
    丸山記念研究奨励賞受賞講演  2016/04
  • ピロールを用いた新しいπ電子系化合物の開発  [Invited]
    日本化学会中国四国支部大会 若手セッション「中国四国地方から発信する有機化学の未来」  2015/11
  • ピロールを用いた新しいπ電子系の構築と物性  [Invited]
    九州大学 先導物質化学研究所講演会  2015/11
  • ピロールを用いた新規π電子系の創製と機能開拓  [Invited]
    大阪府立大学 21世紀科学研究機構、分子エレクトロニックデバイス研究所 第17回研究会 RIMEDシーズ発掘講演会  2015/11
  • ピロール縮環アザコロネンの合成と物性  [Not invited]
    高瀬雅祥, 沖 光脩, 田川和成, 成田智幸, 西長 亨, 森 重樹, 奥島鉄雄, 宇野英満
    分子アーキテクトニクス第6回研究会  2015/10
  • 機能性π共役分子の合成と物性  [Invited]
    愛媛大学工学部 応用化学セミナー  2015/06
  • Synthesis and Properties of Pyrrole-containing Functional π-Electron Systems  [Invited]
    Masayoshi Takase
    Collaborative Conference on 3D and Materials Research (CC3DMR) 2015  2015/06
  • Pyrrole-containing π-Electron Materials: Design, Synthesis and Properties  [Invited]
    Masayoshi Takase
    Ulsan National Institute of Science and Technology  2015/06
  • Pyrrole-fused Azacoronenes with Various Redox States  [Invited]
    Masayoshi Takase
    The 227th Electrochemical Society Meeting (ECS Meeting)  2015/05
  • Synthesis and Physical Properties of Pyrrole-fused Azacoronenes  [Invited]
    Masayoshi Takase
    8th Singapore International Chemistry Conference (SICC 8)  2014/12
  • Pyrrole-fused Azacoronenes with Various Redox States  [Not invited]
    M. Takase, T. Narita, T. Nishinaga, K. Nomura
    International Conference on Synthetic Metals (ICSM 2014)  2014/07
  • Pyrrole-fused Azacoronenes with Various Redox States  [Not invited]
    M. Takase, T. Narita, T. Nishinaga, K. Nomura
    International Conference on Porphyrin and Phthalocyanines (ICPP-8)  2014/06
  • Pyrrole-fused Azacoronenes with Various Redox States  [Invited]
    Masayoshi Takase
    Energy Material Nanotechnology Meeting (EMN east meeting)  2014/05
  • 非局在型ビラジカル構造を有するピロール縮環アザコロネンの合成と物性  [Not invited]
    高瀬雅祥, 成田智幸, 藤田 渉, 西長 亨, 野村琴広
    日本化学会第94春季年会 B講演  2014/03
  • ピロールを基本骨格に用いた機能性π共役分子の合成と物性  [Invited]
    野口遵研究所  2014/03
  • ピロールを用いた芳香族求核置換反応を鍵とする機能性分子の合成と物性  [Not invited]
    高瀬雅祥, 吉田尚史, 成田智幸, 西長 亨, 伊與田正彦
    第24回基礎有機化学討論会  2013/09
  • Synthesis and Properties of Pyrrole-fused Azacoronenes in Neutral and Oxidation States  [Invited]
    Masayoshi Takase
    International Conference on Emerging Advanced Nanomaterials (ICEAN 2012)  2012/10
  • Pyrrole-fused Azacoronenes: Influence of Dialkoxyphenyl Rings on Optical and Electronic Properties in Neutral and Oxidation States  [Not invited]
    M. Takase, T. Narita, T. Nishinaga, K. Nomura, K. Müllen
    IUMRS-International Conference on Electronic Materials (IUMRS-ICEM 2012)  2012/09
  • 機能性π共役系分子の合成と物性: 放射状から環状分子、ナノグラフェンまで  [Invited]
    奈良先端科学技術大学院大学 光ナノサイエンス特別講義  2012/06
  • ドナー・アクセプター分離型シクロファン類の合成と物性  [Not invited]
    稲邊あゆみ, 高瀬雅祥, 西長 亨, 野村琴広
    第92回春季年会  2012/03
  • Synthesis and Properties of Pyrrole-fused Azacoronene Family in Neutral and Oxidation States  [Not invited]
    M. Takase, T. Narita, T. Nishinaga, K. Nomura, K. Müllen
    International Symposium on Electronic/Optic Functional Molecules (ISEOFM2012)  2012/03
  • Pyrrole-containing Functional π-Electron Materials  [Invited]
    Masayoshi Takase
    Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences  2012/03
  • ピロール含有機能性π共役系分子の合成と物性  [Invited]
    住友化学株式会社 先端材料探索研究所 講演会  2012/02
  • Pyrrole-containing π-Electron Materials: Design, Synthesis, and Properties 2  [Invited]
    Masayoshi Takase
    Institute of Chemistry, Chinese Academy of Sciences  2011/10
  • Pyrrole-containing π-Electron Materials: Design, Synthesis, and Properties  [Invited]
    Masayoshi Takase
    Beijing University of Chemical Technology  2011/10
  • 機能性π共役系分子の合成と物性: 放射状から環状分子、ナノグラフェンまで  [Invited]
    立命館大学 第23回超分子創製化学セミナー  2010/08
  • 規則的なナノサイズ空孔を有する含窒素グラフェンシートの構築  [Invited]
    花王芸術・科学財団 第12回助成研究発表会  2010/06
  • ナノグラフェンの合成と機能化  [Invited]
    第3回有機π電子系シンポジウム  2009/12
  • The 3rd International Symposium on the Synthesis and Application of Curved Organic π-Molecules & Materials  [Not invited]
    Masayoshi Takase
    Oxford, UK


Industrial Property Rights

Awards & Honors

  • 2016/04 第7回丸山記念研究奨励賞
    受賞者: 高瀬雅祥
  • 2014/01 有機合成化学協会 昭和電工研究企画賞
    受賞者: 高瀬雅祥
  • 2008/01 有機合成化学協会 DIC研究企画賞
    受賞者: 高瀬雅祥

Research Grants & Projects

  • 様々な次元性を有する含窒素ナノカーボンの創出と機能開拓
    日本学術振興会:科学研究費助成事業 基盤研究(B)
    Date (from‐to) : 2020/04 -2024/03 
    Author : 高瀬 雅祥
  • 曲面構造を有する拡張π電子系材料の創出と機能開拓
    Date (from‐to) : 2020/04 -2021/03 
    Author : 高瀬雅祥
  • Japan Society for the Promotion of Science:Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C)
    Date (from‐to) : 2016/04 -2019/03 
    Author : Takase Masayoshi
    The synthesis and characterization of novel pyrrole-containing nanographenes were performed, which was synthesized by using aromatic nucleophilic substitution of pyrrole toward electron-deficient aromatics and successive oxidative cyclodehydrogenation. Through a series of study, the synthesis of curved π-electron compounds and anti aromatic compounds was succeeded. The compounds showed stable redox properties compared to previously known nanographene, resulted in the isolation of not only neutral species but also radical cations and diction. The structure-property relationships of the newly obtained compounds were conducted.
  • オリゴピロール類を用いた不可視性近赤外吸収色素の開発
    Date (from‐to) : 2017/10 -2018/09 
    Author : 高瀬雅祥
  • Japan Society for the Promotion of Science:Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
    Date (from‐to) : 2013/06 -2018/03 
    Author : Uno Hidemitsu, MORI Shigeki, OGAWA Takuji, IE Yutaka, SUGIMOTO Nobuaki
    Electric measurement of single molecules which pi-systems were altered by external stimuli such as heat, light, acid, etc. was planned. Bicyclo[2.2.2]octadiene ring system was chosen as such an external-stimulus-changeable moiety and porphyrin, and hexapyrrolohexaazacoronene (HPHAC) were chosen as such pi-systems. In bisthiaporphyrins fused with BCOD and benzene rings, their macrocyclic ring current routes were altered from on a long axis to on short axes by protonation.
  • 含窒素拡張π電子系化合物の構築と機能開拓
    Date (from‐to) : 2015/10 -2016/09 
    Author : 高瀬雅祥
  • 不可視性と近赤外吸収特性を有する新規オリゴピロール類の開発
    Date (from‐to) : 2015/10 -2016/09 
    Author : 高瀬雅祥
  • ピロールの特異な反応性を利用した機能性π共役分子の開発
    Date (from‐to) : 2014/03 -2016/03 
    Author : 高瀬雅祥
  • Japan Society for the Promotion of Science:Grants-in-Aid for Scientific Research Grant-in-Aid for Young Scientists (B)
    Date (from‐to) : 2013/04 -2015/03 
    Author : TAKASE Masayoshi
    In this study, we have mainly studied on the molecular design and physical properties of two novel pi-electron systems with peculiar electron structures. (1) Pyrrole-fused azacoronenes with directly attached carbonyl groups were newly synthesized and they showed characteristic NIR absorption in the spectra. Combined with other measurements and calculations, it is suggested that new pi-systems had stable open-shell character in their neutral states. (2) pi-electron donor and acceptor segregated pi-conjugated oligomers were synthesized with naphthobipyrrole as a donor and fluorobenzene as an acceptor. In the lower temperature the segregated structures became clearly.
  • Japan Society for the Promotion of Science:Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (A)
    Date (from‐to) : 2010/05 -2015/03 
    Author : IYODA Masahiko, TAKASE Masayoshi, HASEGAWA Masashi, OTANI Hiroyuki, SHIMIZU Hideyuki
    In this project, we have developed a new concept for the construction of organic supramolecular nanoassembly and prepared key organic pi-electron systems for the studies on their multifunctional properties. We have successfully synthesized a series of giant conjugated macrocycles and constructed their self-assembled nanostructures. The most remarkable properties were obtained from pi-expanded macrocyclic oligothiophene 6-mer and 8-mer. The 6-mer showed a thermally reversible polymorphism, which was applied to either fluorescence switching or switching of field effect transistor (FET) activity and electrical conductivity. The 8-mer formed a Saturn-like complex with C60 in the solid state, and this complex exhibited repeatable and stable instantaneous response of photocurrent.
  • 特異な分極構造を有する新規π共役系化合物の創出
    科研費 若手研究(B)
    Date (from‐to) : 2011/04 -2013/03 
    Author : 高瀬雅祥
  • 分離積層型導電性二重らせんポリマー
    Date (from‐to) : 2011/04 -2012/03 
    Author : 高瀬雅祥
  • 含窒素グラフェン類の合成化学的構築とその新奇機能
    Date (from‐to) : 2010/04 -2012/03 
    Author : 高瀬雅祥
  • Japan Society for the Promotion of Science:Grants-in-Aid for Scientific Research Grant-in-Aid for Young Scientists (B)
    Date (from‐to) : 2011 -2012 
    Author : TAKASE Masayoshi
    In this study, we have studied on the synthesis and physical characterization of novel π-electron materials with peculiar electron structures in their neutral and redox states. As the results (1) a series of extended disk-shaped π-system composed of pyrroles and benzenes were synthesized and characterized, and (2) conceptually new donor-acceptor segregated cyclophanes were developed.
  • 含窒素巨大π共役系分子の構築と物性
    Date (from‐to) : 2010/04 -2011/03 
    Author : 高瀬雅祥
  • 含窒素グラフェン類の合成化学的構築とその新奇機能
    Date (from‐to) : 2010/04 -2011/03 
    Author : 高瀬雅祥
  • 明確な構造のナノサイズ空孔を有する含窒素グラフェンシートの創製
    Date (from‐to) : 2009/04 -2011/03 
    Author : 高瀬雅祥
  • 有機太陽電池を指向した星形ドナー・アクセプターπシステムの構築
    Date (from‐to) : 2009/04 -2010/03 
    Author : 高瀬雅祥
  • ドナー・アクセプター連結スターバーストπシステムの構築
    Date (from‐to) : 2009/04 -2010/03 
    Author : 高瀬雅祥
  • 規則的なナノサイズ空孔を有する含窒素グラフェンシートの構築
    Date (from‐to) : 2009/04 -2010/03 
    Author : 高瀬雅祥
  • 窒素含有グラフェンシート構造体の開発
    科研費 若手研究(スタートアップ)
    Date (from‐to) : 2008/10 -2010/03 
    Author : 高瀬雅祥
  • ジチオラートをアンカー部位とする巨大πドナーおよび分子ファイバーの構築と機能
    日本学術振興会:科学研究費助成事業 特定領域研究
    Date (from‐to) : 2008 -2009 
    Author : 伊與田 正彦, 高瀬 雅祥
    我々これまでに、巨大共役π電子系およびそれらの超分子会合体を構築して、その構造と機能を研究してきた。本課題においては、申請者がこれまで調べてこなかった分子と電極の接合を、申請者の化合物を使って調べることを目的とした。具体的には、金電極と硫黄原子との化学結合をより強固で指向性をもったものとするために、ジチオラートをアンカー部位にもつπドナーと金電極接合系分子の設計・合成を行った。さらに参照化合物の合成も行った。中央のベンゼン環には、溶媒への溶解性を考慮し、長鎖アルキル基を導入した。これらの化合物は、電極間に同じ長さのπ共役パスを有しながらも、多点連結に伴ってその共役パスの数が異なるという特徴を有している。解析手法の発達に伴い単分子電導を明らかにされた報告例は増えつつあるが、このような多点連結、および電導(共役)パスの数に伴う電導性への影響を検討した例はほとんどなく、本系がその一例となり得る。現在、木口准教授(東工大)にこれら分子の単分子電導測定を依頼中であり、これら分子の合成については日本化学会第90春季年会にて発表を行った。 一方、上記の系とは別に、谷口准教授(阪大産研)との共同研究で、光スイッチ単分子のデバイスの構築に取り込んだ。光スイッチ分子には、耐久性があり、かつその開環体と閉環体とで大きくそのπ共役系を変化させるジアリルエテン誘導体の設計・合成を行った。ジクロロメタン中、可視光(532nm)および紫外光(350nm)照射のもと機械的破断接合過程における電導度測定を行ったところ、開環体において2mG_0、閉環体において4m G_0であるという値をこれまでに得ている。
  • Japan Society for the Promotion of Science:Grants-in-Aid for Scientific Research Grant-in-Aid for Young Scientists (Start-up)
    Date (from‐to) : 2008 -2009 
    Author : TAKASE Masayoshi
    We have newly designed and synthesized tri-, tetra-, and hexa-substituted pyrrole-fused TTF derivatives. Self-assembly of these molecules gave fiber and particle structures from proper solutions and their electric conductivities under iodine vapor indicated higher than that of the film state by an order of magnitude. Similar reaction with ditopic TTF derivatives gave insoluble materials probably due to the formation of three-dimensional porous networks.
  • Japan Society for the Promotion of Science:Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (B)
    Date (from‐to) : 2006 -2008 
    Author : IYODA Masahiko, NISHINAGA Tohru, TAKASE Masayoshi
    近年、ナノスケールの共役系に関する研究が急速に発展している。このようなナノ分子は、溶液中で自己組織化して多量体を形成したり、その分子内の空孔に小さなπ共役分子を取り込んで包接錯体を形成する。また、π電子系を鎖状につなげた系では、ナノスケールのらせん構造ができるので、大きな二次構造をもつ分子となり、非常に大きな旋光度も予想される。このようなナノスケールの分子には、上記の性質のほかに、磁性-伝導性-光物性という複合機能も発現する。そこで申請者らがこれまでに研究してきた比較的大きなπ共役系の機能の探求から始めて、徐々に分子サイズを大きくすることにより、ナノπ共役系の新しい機能を調べることを目的として研究を行った。 先ず、共役π電子系の化学に基づいて合成反応を組み立てることによって、環状ポリフェニレン、環状ポリへテロアレーンおよび放射状ドナー分子を合成した。次いで、大きなπ電子系化合物の自己組織化と機能を調べ、これらの系から得られる分子ワイヤーの構造と機能を解明した。環状ポリフェニレンおよび環状ポリへテロアレーンは、ドーナツ型分子であり、内部に空孔を持つので、その環サイズによって小分子から大きなフラーレンのような分子を包接することが期待できる。また、放射状πドナーは、ほぼ平面構造を持った分子であるから、溶液中および結晶中で自己組織化して多量体を形成したり、カラム構造を作ると予想される。そこで、このような新規積層構造を持つ分子のスイッチ機能および光化学材料としての可能性を検討した。さらに、環状ポリへテロアレーンおよび放射状πドナー分子に関しては、これらの分子の中性状態における物性を調べたのち、そのCT錯体とラジカル塩を調製して、伝導性と磁性についても調べた。
  • 超分子鋳型効果を用いた有機ナノチューブの創製
    Date (from‐to) : 2003/10 -2004/03 
    Author : 高瀬雅祥

Social Contribution

  • Date (from-to) : 2019/12/05-2019/12/07
    Role : Organizing member 松山大学 カルフール・ホール
  • Date (from-to) : 2018/11/17-2018/11/18
    Role : Organizing member
    Sponser, Organizer, Publisher  : 日本化学会中国四国支部
  • 第78回パネル討論会 「ポルフィリノイド化学の進歩と展望」
    Date (from-to) : 2018/07/21-2018/07/21
    Role : Organizing member
    Sponser, Organizer, Publisher  : 有機合成化学協会中国四国支部
  • 第8回分子アーキテクトニクス研究会
    Date (from-to) : 2017/12/04-2017/12/05
    Role : Organizing member
    Sponser, Organizer, Publisher  : 日本化学会 分子アーキテクトニクス研究会
  • 新学術領域研究 分子アーキテクトニクス 第9回領域会議
    Date (from-to) : 2017/12/03-2017/12/03
    Role : Organizing member
    Sponser, Organizer, Publisher  : 新学術領域研究 分子アーキテクトニクス
  • Date (from-to) : 2017/11/24-2017/11/24
    Role : Organizing member
    Sponser, Organizer, Publisher  : 臭素化学懇話会
  • Date (from-to) : 2015/09/24-2015/09/26
    Role : Organizing member
    Sponser, Organizer, Publisher  : 基礎有機化学会
  • International Workshop on Molecular Architectonics
    Date (from-to) : 2015/08/03-2015/08/06
    Role : Organizing member
    Sponser, Organizer, Publisher  : 新学術領域研究 分子アーキテクトニクス
  • 第35回有機典型元素化学討論会
    Date (from-to) : 2008/12/11-2008/12/13
    Role : Organizing member
    Sponser, Organizer, Publisher  : 有機典型元素化学討論会実行委員会




  • 2019, the first semester, under graduate, 卒業研究Ⅰ
  • 2019, the first semester, under graduate, 化学Ⅱ
  • 2019, the first semester, master course, 分子科学高等実習Ⅱ
  • 2019, the first semester, master course, 化学ゼミナールⅠ
  • 2019, the first semester, master course, 化学ゼミナールⅢ
  • 2019, the first semester, master course, 分子科学課題演習I

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