“反芳香環"が創るπ空間の性質とその応用

• Project Area: Emergence of highly elaborated pai-space and its function
• Project/Area Number: 21108519
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tokyo Metropolitan University
• Principal Investigator: 西長 亨 首都大学東京, 大学院・理工学研究科, 准教授 (30281108)
• Project Period (FY): 2009 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2010: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2009: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
• Keywords: シクロオクタテトラエン / 反芳香族性 / 結晶構造解析 / 分子間相互作用 / 電界効果トランジスタ / 両極性トランジスタ

Research Abstract

近年、平面構造を強制したシクロオクタテトラエン(COT)の反芳香族性に関する研究が注目を集めている。さらにこのような"反芳香環"を2枚向かい合わせた分子において、空間を介する相互作用により芳香族性が誘起されるという理論研究が最近相次いで報告されている。このような背景のもと、本研究では、我々のこれまでの平面COTの反芳香族性に関する研究、ならびに含硫黄π共役系の基礎物性に関する研究および有機FETへの応用研究を基に、これらの独創的な成果を発展的に融合させることにより、"反芳香環"によって誘起される芳香族性のπ空間に関する基礎および応用研究を推進することを目的とする。最終年度は嵩高い置換基を用いることなく平面構造を実現することが可能な硫黄架橋の環状チオフェン4量体に種々の置換基を導入し、その中でトリイソプロピルシリルエチニル体の単結晶の素子で高い移動度(μh=0.40andμe=0.18cm^2V^<-1>s^<-1>)で両極性挙動を示すことを明らかにした。

Research Products

• [Journal Article] Sterically congested pyrrole-fused tetrathiafulvalene decamers as highly conductive amorphous molecular materials (2012)
  • Author(s): M.Takase, N.Yoshida, T.Narita, T.Fujio, T.Nishinaga, M.Iyoda
  • Journal Title: RSC Advances Volume: 2 Pages: 3221-3224
  • Peer Reviewed
• [Journal Article] Mcmurry Coupling Of Diformyldithienylacetylene : Synthesis Of [24]-, [36]-, And [48] Annulenes Composed Of Thiophene, Acetylene, And Ethylene Units (2011)
  • Author(s): M.Iyoda, P.Huang, T.Nishiuchi, M.Takase, T.Nishinaga
  • Journal Title: Heterocycles Volume: 82 Pages: 1143-1149
  • Peer Reviewed
• [Journal Article] Self-assembly and nanostructure formation of amphiphilic 4,5-bis(2-pyridylethynyl)tetrathiaful valenes (2011)
  • Author(s): E.Isomura, T.Nishinaga, M.Iyoda
  • Journal Title: Supramol.Chem. Volume: 23 Pages: 304-309
  • Peer Reviewed
• [Journal Article] Synthesis and Nanostructures of Cyclic Triphenylene Trimers Having Long Alkyl and Alkoxy Side Chains (2011)
  • Author(s): Y.Hanai, M.J.Rahman, J.Yamakawa, M.Takase, T.Nishinaga, M.Hasegawa, K.Kamada, M.Iyoda
  • Journal Title: Chem.Asian J. Volume: 6 Pages: 2940-2945
  • Peer Reviewed
• [Journal Article] Structural, Optical, and Electronic Properties of a Series of 3,4-Propylenedioxythiophene Oligomers in Neutral and Various Oxidation State (2011)
  • Author(s): C.Lin, T.Endo, M.Takase, M.Iyoda, T.Nishinaga
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 11339-11350
  • Peer Reviewed
• [Journal Article] Star-Shaped Pyrrole-Fused Tetrathiafulvalene Oligomers : Synthesis and Redox, Self-Assembling, and Conductive Properties (2011)
  • Author(s): M.Takase, N.Yoshida, T.Nishinaga, M.Iyoda
  • Journal Title: Org.Lett. Volume: 13 Pages: 3896-3899
  • Peer Reviewed
• [Journal Article] Synthesis and structural, electronic, optical and FET properties of thiophene-pyrrole mixed hexamers end-capped with phenyl and pentafluorophenyl groups (2011)
  • Author(s): T.Nishinaga, T.Miyata, M.Tateno, M.Koizumi, M.Takase, M.Iyoda, N.Kobayashi, Y.Kunugi
  • Journal Title: J.Mater.Chem. Volume: 21 Pages: 14959-14966
  • Peer Reviewed
• [Journal Article] Single Crystal Organic Field-effect Transistors Based on 2,8-Diphenyl and Dinaphthyl Chrysenes (2011)
  • Author(s): Y.Kunugi, T.Arai, N.Kobayashi, H.Otsuki, T.Nishinaga, K.Okamoto
  • Journal Title: J.Photopolymer Sci.Technol. Volume: 24 Pages: 345-348
  • Peer Reviewed
• [Journal Article] Star-Shaped Oligothiophenes with Unique Photophysical Properties and Nanostmctures (2010)
  • Author(s): T.Narita, M.Takase, T.Nishinaga, M.Iyoda, K.Kamada, K.Ohta
  • Journal Title: Chem.Eur.J. Volume: 16 Pages: 12108-12113
  • Peer Reviewed
• [Journal Article] Biradical Character of Linear π-Conjugated Oligomer Dications Composed of Thiophene, Pyrrole and Methylthio End-Capping Units (2010)
  • Author(s): T.Nishinaga, M.Tateno, M.Fujii, W.Fujita, M.Takase, M.Iyoda
  • Journal Title: Org.Lett. Volume: 12 Pages: 5374-5377
  • Peer Reviewed
• [Journal Article] Structural, Electronic and Magnetic Properties of Cu(II) Complexes of 2-Substituted Tropones Bearing Ferrocenyl Group at 5-Position (2010)
  • Author(s): T.Nishinaga, T.Aono, E.Isomura, S.Watanabe, Y.Miyake, A.Miyazaki, T.Enoki, H.Miyasaka, H.Otani, M.Iyoda
  • Journal Title: Dalton Trans. 39 Pages: 2293-2300
  • Peer Reviewed
• [Journal Article] Synthesis of Bitetrathiafulvalene with FeCl_3-Mediated Homocoupling of Tetrathiafulvalenylmagnesium Bromide and Formation of Nanostructures from Bitetrathiafulvalene having Long Alkylthio Chains (2010)
  • Author(s): Y.Honna, E.Isomura, H.Enozawa, M.Hasegawa, M.Takase, T.Nishinaga, M.Iyoda
  • Journal Title: Tetrahedron Lett. 51 Pages: 679-682
  • Peer Reviewed
• [Journal Article] Cyclic Tetrathiophenes Planarized by Silicon and Sulfur Bridges Bearing Antiaromatic Cyclooctatetraene Core : Syntheses, Structures, and Properties (2010)
  • Author(s): T.Ohmae, T.Nishinaga, W, Mo, M.Iyoda
  • Journal Title: J.Am.Chem.Soc. 132 Pages: 1066-1074
  • Peer Reviewed
• [Journal Article] Recent Studies on the Aromaticity and Antiaromaticity of Planar Cyclooctatetraene (2010)
  • Author(s): T.Nishinaga, T.Ohmae, M.Iyoda
  • Journal Title: Symmetry 2 Pages: 76-97
  • Peer Reviewed
• [Journal Article] Synthesis and Properties of Octithiophene Dication Sterically Segregated by Annelation with Bicyclo[2.2.2]octene Units (2010)
  • Author(s): T. Nishinaga, D.Yamazaki, M.Tateno, M.Iyoda, K.Komatsu
  • Journal Title: Materials 3 Pages: 2037-2052
  • Peer Reviewed
• [Journal Article] Small Difference in Side Chain of Tetrathiafulvaleno[18]annulenes Causing Magnetic Alignment in Solid State and Temperature Hysteresis in Aqueous Tetrahydrofuran Solution (2009)
  • Author(s): H.Enozawa, M.Hasegawa, E.Isomura, T.Nishinaga, T.Kato, M.Yamato, T.Kimura, Masahiko Iyoda
  • Journal Title: Chem.Phys.Chem. 10 Pages: 2607-2611
  • Peer Reviewed
• [Presentation] Antiaromatic Cyclooctatetraene-Based Semiconductors for Ambipolar Field Effect Transistors with High and Balanced Mobility (2011)
  • Author(s): T.Ohmae, K.Aita, M.Takase, M.Iyoda, T.Nishinaga, T.Arai, Y.Kunugi
  • Organizer: 10th International Symposium on Functional pi-Electron Systems
  • Place of Presentation: Beijing, China
  • Year and Date: 2011-10-14
• [Presentation] 高移動度かつバランスの良い両極性FET性能を示す平面COT誘導体の性質 (2011)
  • Author(s): 大前武士, 相田一成, 高瀬雅祥, 伊與田正彦, 西長亨, 新井竜也, 功刀義人
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: つくば
  • Year and Date: 2011-09-21
• [Presentation] Antiaromatic planar cyclooctatetraenes : A new strategy for ambipolar organic field effect transistors (2011)
  • Author(s): T.Nishinaga, T.Ohmae, K.Aita, M.Takase, M.Iyoda, T.Arai, Y.Kunugi
  • Organizer: 14th International Symposiun on Novel Aromatic Compounds
  • Place of Presentation: Eugene, Oregon
  • Year and Date: 2011-07-25
• [Presentation] 平面COT構造を有する環状チオフェン四量体誘導体の性質 (2011)
  • Author(s): 相田一成, 大前武士, 高瀬雅祥, 伊與田正彦, 西長亨
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川
• [Presentation] Relationship between structure and antiaromaticity of planar cyclooctatetraenes (2010)
  • Author(s): T.Nishinaga
  • Organizer: Pacifichem 2010
  • Place of Presentation: Honolulu
  • Year and Date: 2010-12-16
• [Presentation] 平面シクロオクタテトラエン誘導体の合成とFET特性 (2010)
  • Author(s): 大前武士, 西長亨, 高瀬雅祥, 伊與田正彦, 新井竜也, 功刀義人
  • Organizer: 第21回基礎有機化学討論会
  • Place of Presentation: 名古屋
  • Year and Date: 2010-09-10
• [Presentation] 反芳香環を有する環状チオフェン4量体の誘導体の合成とFET特性 (2010)
  • Author(s): 大前武士、西長亨、高瀬雅祥、伊与田正彦、小林宣仁、功刀義人
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪
  • Year and Date: 2010-03-27
• [Presentation] 反芳香環を有するチオアルキル置換ジチエノチオフェン2量体の合成と性質 (2010)
  • Author(s): 野澤優斗、大前武士、西長亨、高瀬雅祥、伊与田正彦
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪
  • Year and Date: 2010-03-27
• [Presentation] 環状8π電子系を有するジチエノチオフェン2量体のFET特性 (2009)
  • Author(s): 大前武士、西長亨、高瀬雅祥、伊与田正彦、小林宣仁、猪狩光章、功刀義人
  • Organizer: 第36回有機典型元素化学討論会
  • Place of Presentation: 鳥取
  • Year and Date: 2009-12-11
• [Presentation] 反芳香環"が創るπ空間の性質とその応用 (2009)
  • Author(s): 西長亨
  • Organizer: 新学術領域研究「π空間」第2回公開シンポジウム
  • Place of Presentation: 京都
  • Year and Date: 2009-08-27
• [Presentation] Synthesis and Properties of Sulfur Bridged Cyclic Tetrathiophene Bearing an Antiaromatic Cyclooctatetraene Rine (2009)
  • Author(s): Takeshi Ohmae, Tohru Nishinaga, Masahiko Iyoda
  • Organizer: 13^<th> International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Luxembourg
  • Year and Date: 2009-07-20
• [Book] PEDOTの材料物性とデバイス応用(分担執筆) (2012)
  • Author(s): 西長亨, 伊与田正彦
  • Total Pages: 405
  • Publisher: サイエンス&テクノロジー
• [Remarks]
  • URL: http://www.sci.metro-u.ac.jp/chem/org/