Synthesis and Electronic Structure Elucidation of Multi-Phenalenyl Compounds linked by acetylene

2008 Fiscal Year Final Research Report

• Project/Area Number: 19550039
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: KUBO Takashi Osaka University, 大学院・理学研究科, 教授 (60324745)
• Project Period (FY): 2007 – 2008
• Keywords: 強相関電子系 / 磁性 / 光物性 / 有機導体 / フェナレニル

Research Abstract

一般に反応活性中間体として扱われている一重項ビラジカル種を、不対電子非局在化能の高いフェナレニル骨格を利用して熱力学的に安定化させ結晶として単離し、固体物性すなわち分子集合状態の物性を明らかにした。精査の結果、一重項ビラジカルは分子内と分子間で不対電子間相互作用を共存させる、という従来にはない概念を見出した。得られた化合物は両性FET特性を示し、また大きな二光子吸収断面積を有するなど、一重項ビラジカル種の優れた機能も明らかとなった。

Research Products

• [Journal Article] Tetrahedral Oligothiophenes ; Synthesis, X-ray Analysis, and Optoelectronic Properties of Highly Symmetrical, 3D-Branched Oligothiophenes. Matsumoto (2008)
  • Author(s): K. ; Tanaka, T. ; Kugo, S. ; Inagaki, T. ; Hirao, Y. ; Kurata, H. ; Kawase, T. ; Kubo, T.
  • Journal Title: Chem. Asian J. 3 Pages: 2024-2032
• [Journal Article] Theoretical study of third-order nonlinear optical properties in square nanographenes with open-shell singlet ground states. Nakano (2008)
  • Author(s): M. ; Nagai, H. ; Fukui, H. ; Yoneda, K. ; Kishi, R. ; Takahashi, H. ; Shimizu, A. ; Kubo, T. ; Kamada, K. ; Ohta, K. ; Champagne, B. ; Botek, E. Chem
  • Journal Title: Phys. Lett. 467 Pages: 120-125
• [Journal Article] Electronic structure of 2, 5, 8-tri-tert-butylphenalenyl radical studied by He(I) photoelectron spectroscopy (2008)
  • Author(s): Kubota, M. ; Kobayashi, T. ; Kubo, T. ; Nakasuji, K.
  • Journal Title: J. Electron Spectrosc. Relat. Phenom. 165 Pages: 11-14
• [Journal Article] Theoretical Study on Second Hyperpolarizabilities of Singlet Diradical Square Planar Nickel Complexes Involving o-Semiquinonato Type Ligands (2008)
  • Author(s): Fukui, H. ; Kishi, R. ; Minami, T. ; Nagai, H. ; Takahashi, H. ; Kubo, T. ; Kamada, K. ; Ohta, K. ; Champagne, B. ; Botek, E. ; Nakano, M.
  • Journal Title: J. Phys. Chem. A 112 Pages: 8423-8429
• [Journal Article] Intermolecular interaction effects on the second hyperpolarizability of open-shell singlet diphenalenyl radical dimer (2008)
  • Author(s): Nakano, M. ; Takebe, A. ; Kishi, R. ; Fukui, H. ; Minami, T. ; Kubota, K. ; Takahashi, H. ; Kubo, T. ; Kamada, K. ; Ohta, K. ; Champagne, B. ; Botek, E.
  • Journal Title: Chem. Phys. Lett. 454 Pages: 97-104
• [Journal Article] Theoretical study on the second hyperpolarizability of open-shell singlet one-dimensional systems with a charged defect (2008)
  • Author(s): Takebe, A., Nakano, M., Kishi, R., Nate, M., Takahashi, H., Kubo, T., Kamada, K., Ohta, K., Champagne, B., Botek, E.
  • Journal Title: Chem. Phys. Lett. 451 Pages: 111-115
• [Journal Article] Finite-Field Spin-Flip Configuration Interaction Calculation of the Second Hyperpolarizabilities of Singlet Diradical Systems (2007)
  • Author(s): Kishi, R. ; Nakano, M. ; Ohta, S. ; Takebe, A. ; Nate, M. ; Takahashi, H. ; Kubo, T. ; Kamada, K. ; Ohta, K. ; Champagne, B. ; Botek, E.
  • Journal Title: J. Chem. Theor. Comp. 3 Pages: 1699-1707
• [Journal Article] Second Hyperpolarizabilities of Singlet Polycyclic Diphenalenyl Radicals : Effects of the Nature of the Central Heterocyclic Ring and Substitution to Diphenalenyl Rings (2007)
  • Author(s): Nakano, M. ; Nakagawa, N. ; Kishi, R. ; Ohta, S. ; Nate, M. ; Takahashi, H. ; Kubo, T. ; Kamada, K. ; Ohta, K. ; Champagne, B. ; Botek, E. ; Morita, Y. ; Nakasuji, K. ; Yamaguchi, K.
  • Journal Title: Phys. Chem. A. 111(37) Pages: 9102-9110
• [Journal Article] Relationship between Third-Order Nonlinear Optical Properties and Magnetic Interactions in Open-Shell Systems : A New Paradigm for Nonlinear Optics (2007)
  • Author(s): Nakano, M. ; Kishi, R. ; Ohta, S. ; Takahashi, H. ; Kubo, T. ; Kamada, K. ; Ohta, K. ; Botek, E. ; Champagne, B.
  • Journal Title: Phys. Rev. Lett. 99 Pages: 033001-1-4
• [Journal Article] First and second hyperpolarizabilities of donor-acceptor disubstituted diphenalenyl radical systems. (2007)
  • Author(s): Nakano, M. ; Ohta, S. ; Tokushima, K. ; Kishi, R. ; Kubo, T. ; Kamada, K. ; Ohta, K. ; Champagne, B. ; Botek, B. ; Takahashi, H.
  • Journal Title: Chem. Phys. Lett. 443 Pages: 95-101
• [Journal Article] Ambipolar Organic Field-Effect Transistors Based on a Narrow Bandgap Semiconductor with Balanced Hole and Electron Mobilities (2007)
  • Author(s): Chikamatsu, M. ; Mikami, T. ; Chisaka, J. ; Shimizu, A. ; Kubo, T. ; Morita, Y. ; Nakasuji, K. ; Yoshida, Y. ; Azumi, R. ; Yase, K.
  • Journal Title: Appl. Phys. Lett. 91 Pages: 043506
• [Journal Article] Syntheses and Characterizations of Acetylene-Linked Bisphenalenyl and Metallic-like Behavior in Its Charge Transfer Complex (2007)
  • Author(s): Kubo, T. ; Goto, Y. ; Uruichi, M. ; Yakushi, K. ; Nakano, M. ; Fuyuhiro, A. ; Morita, Y. ; Nakasuji, K.
  • Journal Title: Chem Asian J. 2 Pages: 1370-1379
• [Journal Article] Theoretical Study on the Second Hyperpolarizabilities of Phenalenyl Radical Systems Involving Acetylene and Vinylene Linkers : Diradical Character and Spin Multiplicity Dependences. (2007)
  • Author(s): Ohta, S. ; Nakano, M. ; Kubo, T. ; Kamada, K. ; Ohta, K. ; Kishi, R. ; Nakagawa, N. ; Champagne, B. ; Botek, E. ; Takebe, A. ; Umezaki, S.-y. ; Nate, M. ; Takahashi, H. ; Furukawa, S.-i. ; Morita, Y. ; Nakasuji, K. ; Yamaguchi, K. J.
  • Journal Title: Phys. Chem. A. 111(18) Pages: 3633-3641
• [Journal Article] A New Hydrogen-Bonded Charge-Transfer Complex [Ni(Hpydt)2]TNAP ; Synthesis, Structure and Electrical Conductivity (2007)
  • Author(s): Shibahara, S. ; Kitagawa, H. ; Kubo, T. ; Nakasuji, K. Inorg
  • Journal Title: Chem. Comm. 10 Pages: 860-862
• [Journal Article] Strong Two-Photon Absorption of Singlet Diradical Hydrocarbons (2007)
  • Author(s): Kamada, K. ; Ohta, K. ; Kubo, T. ; Shimizu, A. ; Morita, M. ; Nakasuji, K. ; Kishi, R. ; Ohta, S. ; Furukawa, S. ; Takahashi, H. ; Nakano, M.
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 3544-3546
• [Journal Article] Syntheses and Unusual Segregated-Alternated Hybrid Stacking Structure of Hydrogen-Bonded Charge- Transfer Complexes Composed of Bis[2, 3-pyridinedithiolate]Metal Complexes (2007)
  • Author(s): Shibahara, S. ; Kitagawa, H. ; Ozawa, Y. ; Toriumi, K. ; Kubo, T. ; Nakasuji, K.
  • Journal Title: Inorg. Chem. 46 Pages: 1162-1170
• [Presentation] 非局在型一重項ビラジカルにおける不対電子間相互作用の実験的考察 (2009)
  • Author(s): 久保孝史
  • Organizer: 分子研研究会「ビラジカル化学とその展望」
  • Place of Presentation: 分子研(招待講演)
  • Year and Date: 20090305-06
• [Presentation] Theoretical and experimental studies on anti-ferromagnetic (open-shell singlet) ground state of polycyclic aromatic hydrocarbons(招待講演) (2009)
  • Author(s): Takashi KUBO
  • Organizer: Okazaki Conference
  • Place of Presentation: Okazaki Japan
  • Year and Date: 20090221-23
• [Presentation] ビスフェナレニル型一重項ビラジカル種の電子構造 (2008)
  • Author(s): 久保孝史
  • Organizer: 第2回分子科学討論会
  • Place of Presentation: 福岡国際会議場
  • Year and Date: 20080924-27
• [Presentation] ベンゼン環からグラフェンエッジ(ラジカル)状態を作る (2008)
  • Author(s): 久保孝史
  • Organizer: 日本物理学会2008年秋季
  • Place of Presentation: 岩手大学(依頼講演)
  • Year and Date: 20080920-23
• [Presentation] 電子およびプロトンの非局在性を活かしたパイ共役系有機分子の化学 (2008)
  • Author(s): 久保孝史
  • Organizer: 第40回構造有機化学若手の会夏の学校
  • Place of Presentation: 足和田ホテル(招待講演)
  • Year and Date: 20080806-08
• [Presentation] Singlet Biradical Hydrocarbons Based on Bisphenalenyl(招待講演) (2007)
  • Author(s): Takashi KUBO
  • Organizer: Molecular Designs, Syntheses, and Functional Properties, 4^<th> Japanese-Sino Symposium on Organic Chemistry for Young Scientists
  • Place of Presentation: Narita, Japan
  • Year and Date: 20070922-27
• [Presentation] Isolable Singlet Biradicals Based on Bisphenalenyl (2007)
  • Author(s): Takashi KUBO
  • Organizer: Intra- and Inter-molecular Spin-Spin Interaction, 12 ^<th> International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Awaji Island, Japan
  • Year and Date: 20070722-27
• [Presentation] Singlet biradical hydrocarbons based on bisphenalenyl : Syntheses and physical properties associated with biradical character, 1 ^<st> Russian-Japanese Workshop (2007)
  • Author(s): Takashi KUBO
  • Organizer: Open Shell Compounds and Molecular Spin Devices
  • Place of Presentation: Novosibirsk, Russia
  • Year and Date: 20070630-0702
• [Book] みず学への誘い (2008)
  • Author(s): 久保孝史(共著)、大垣一成・江頭靖幸・渡會仁・松村道雄・中辻啓二(編著)
  • Total Pages: 62-77
  • Publisher: 大阪大学出版会
• [Remarks]
  • URL: http://www.chem.sci.osaka-u.ac.jp/lab/kubo/Start.html