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曲面π共役上に高度に非局在化したスピンを有する開設分子の合成

Research Project

Project/Area Number 18655058
Research Category

Grant-in-Aid for Exploratory Research

Allocation TypeSingle-year Grants
Research Field Functional materials chemistry
Research InstitutionOsaka University

Principal Investigator

森田 靖  Osaka University, 理学研究科, 准教授 (70230133)

Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2007: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2006: ¥2,600,000 (Direct Cost: ¥2,600,000)
Keywords曲面π共役 / 開殻分子 / 奇交互炭化水素 / フェナレニル / 非局在性
Research Abstract

C_<60>等の曲面π共役系化合物の存在とその物性がクローズアップされている。これらの性質を分子レベルで理解し発展させるためには、曲面π共役電子系における曲面芳香族性やConcave-ConvexおよびConvex-Convex相互作用等の分子間相互作用の解明が重要である。我々は、曲面π共役上に非局在化した電子スピンを有する空気中でも安定な開殻有機分子を設計・合成し、溶液状態および固体状態における性質を詳細に調査する手法を発案した。
これまでに曲面π共役系閉殻有機分子であるコラヌレンに着目し、6-オキソフェルダジルラジカルやイミノニトロキシドをコラヌレンに結合させた開殻有機分子を設計・合成・単離し、曲面π共役上にスピンが非局在化した安定な開殻有機分子の研究の端緒を開いた。本年度は、フェノキシルラジカル部位をコラヌレンに結合させた開殻有機分子を設計・合成・単離した。電子スピン密度分布のトポロジー的対称性からフェノキシルラジカル結合体では、それまでの分子システムに比べてより多くの電子スピンが曲面π共役系上に非局在化していることが判明した。また、曲面π共役型の中性ラジカルとしては初めての単結晶X線構造解析に成功し、磁気測定を行うことで、分子間の磁気的な相互作用について明らかにした。さらに我々は、フェノキシルラジカル部位を二つコラヌレンに結合させた中性ジラジカルの合成と単離に成功した。そして、分子内のスピン間相互作用や電子スピン密度分布、および単結晶X線構造解析による結晶構造の解明にも成功した。このような成果は、今後の分子設計および当初の研究目標の遂行に大いに貢献した。

Report

(2 results)
  • 2007 Annual Research Report
  • 2006 Annual Research Report
  • Research Products

    (32 results)

All 2008 2007 2006

All Journal Article (21 results) (of which Peer Reviewed: 12 results) Presentation (10 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Curved Aromaticity of a Corannulene-Based Neutral Radical: Crystal Structure and 3D Unbalanced Delocalization of Spin2008

    • Author(s)
      Morita, Y.
    • Journal Title

      Angew. Chem. Int. Ed. 47

      Pages: 2035-2038

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Novel TTF-based Electron-donor with Imidazole-annelation Having Hydrogen-bond and Proton-transfer Abilities2008

    • Author(s)
      Morita, Y.
    • Journal Title

      Chem. Lett. 37

      Pages: 24-25

    • NAID

      10020147536

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Thermochromism in an Organic Crystal Based on the Co-existence of σ- and π-Dimers2008

    • Author(s)
      Morita, Y.
    • Journal Title

      Nature Mater. 7

      Pages: 48-51

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Implementation of Molecular Spin Quantum Computing by Pulsed ENDOR Technique: Direct Observation of Quantum Entanglement and Spinor2007

    • Author(s)
      Sato, K.
    • Journal Title

      Physica E: Low-dimensional Systems and Nanostructures 40

      Pages: 363-366

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Syntheses and Characterizations of Acetylene-Linked Bisphenalenyl and Metallic-like Behavior in Its Charge-Transfer Complex2007

    • Author(s)
      Kubo, T.
    • Journal Title

      Chem. Asian J. 2

      Pages: 1370-1379

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Second Hyperpolarizabilifies of Singlet Polycyclic Diphenalenyl Radicats: Effects of the Nature of the Central Heterocyclic Ring and Substitution to Diphenalenyl Rings2007

    • Author(s)
      Nakano, M.
    • Journal Title

      J. Phys. Chem. A 111

      Pages: 9102-9110

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Zwitterionic p-Radical Involving EDT-TTF-Imidazole and F_4TCNQ: Redox Properties and Self-assembled Structure by Hydrogen-bond and Multiple S…S Interaction2007

    • Author(s)
      Murata, T.
    • Journal Title

      Chem. Commun.

      Pages: 4009-4011

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ambipolar Organic Field-effect Transistors Based on a Low Band Gap Semiconductor with Balanced Hole and Electron Mobilities2007

    • Author(s)
      Chikamatsu, M.
    • Journal Title

      Appl. Phys. Lett. 91

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrogen-Bond Interaction in Organic Conductors: Redox Activation, Molecular Recognition, Structural Regulation, and Proton-Trapsfer in Donor-Acceptor Charge-Transfer Complexes of TTF-Imidazole2007

    • Author(s)
      Murata, T.
    • Journal Title

      J. Am. Chem. Soc. 129

      Pages: 10837-10846

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] TTF-Cytosine Dyad as an Electron-donor Molecule Having Proton-accepting Ability: Formation of Hemiprotonated Cytosine Dimer in I_3-Salt2007

    • Author(s)
      Miyazaki, E.
    • Journal Title

      Chem. Lett. 36

      Pages: 1102-1103

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Control in Spin-delocalization into The 2-Substituted π-Systems in 3-Oxophenalenoxyl Neutral Radicals: Evaluation by Their Dimeric Structures and DFT Calculations2007

    • Author(s)
      Nishida, S.
    • Journal Title

      Tetrahedron 63

      Pages: 7690-7695

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Theoretical Study on the Second Hyperpolarizabilities of Phenalenyl Radical Systems Involving Acetylene and Vinylene Linkers: Dira dical Character and Spin Multiplicity Dependences2007

    • Author(s)
      Ohta, S.
    • Journal Title

      J. Phys. Chem. A 111

      Pages: 3633-3641

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Strong Two-photon Absorption of Singlet Diradical Hydrocarbons2007

    • Author(s)
      Kamada, K.
    • Journal Title

      Angew. Chem. Int. Ed. (印刷中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] CASCI-DFT Study of the Phenalenyl Radical System2007

    • Author(s)
      Ukai, T.
    • Journal Title

      Polyhedron (印刷中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Ethylenedithio-TTF-Imidazole : Construction of Pluri-Dimensional Network by Hydrogen-Bonding and S・・・S Interactions2007

    • Author(s)
      Murata, T.
    • Journal Title

      Multifunctional Conducting Molecular Materials

      Pages: 135-135

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Singlet Biradical Character of Phenalenyl-based Kekule Hydrocarbon with Naphthoquinoid Structure2007

    • Author(s)
      Kubo, T.
    • Journal Title

      Org. Lett. 9

      Pages: 81-81

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Two-Dimensional Networks of Ethylenedithio-Tetrathiafulvalene Derivatives with the Hydrogen-Bonded Functionality of Uracil, and Channel Structure of Its Tetracyanoquinodimethane Complex2006

    • Author(s)
      Morita, Y.
    • Journal Title

      J. Org. Chem. 71

      Pages: 5631-5631

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Origin of The Enhancement of The Second Hyperpolarizability of Singlet Diradical Systems with Intermediate Diradical Character2006

    • Author(s)
      Nakano, M.
    • Journal Title

      J. Chem. Phys. 125

      Pages: 74113-74113

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Second Hyperpolarizabilities (γ) of Open-shell Singlet One-dimensional Systems : Intersite Interaction Effects on The Average Diradical Character and Size Dependences of γ2006

    • Author(s)
      Nakano, M.
    • Journal Title

      Chem. Phys. Lett. 432

      Pages: 473-473

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Second Hyperpolarizabilities of Polycyclic Diphenalenyl Radicals : Effects of para/ortho-Quinoid Structures and Central Ring Modification2006

    • Author(s)
      Nakano, M.
    • Journal Title

      Chem. Phys. Lett. 429

      Pages: 174-174

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Second Hyperpolarizability of Phenalenyl Radical System Involving Acetylene π-Conjugated Bridge2006

    • Author(s)
      Ohta, S.
    • Journal Title

      Chem. Phys. Lett. 420

      Pages: 432-432

    • Related Report
      2006 Annual Research Report
  • [Presentation] 曲面π共役型セミキノンラジカル:アルカリ金属イオンとのキレート配位構造と電子スピン構造の解明2008

    • Author(s)
      小笠原華菜子
    • Organizer
      日本化学会第88季年会
    • Place of Presentation
      東京
    • Related Report
      2007 Annual Research Report
  • [Presentation] Electronic-spin Structure of Neutral Radical Derivatives of Corann ulene having Bowl-shaped and Non-alternant π-Conjugated System2008

    • Author(s)
      Ueda, A.
    • Organizer
      The lst International Global COE Symposium on Bio-Environmental Chemistry
    • Place of Presentation
      大阪
    • Related Report
      2007 Annual Research Report
  • [Presentation] 曲面型の非交互π共役系における三次元的な電子スピン構造の解明:コラヌレンを基盤とした安定中性ラジカルの合成と物性2007

    • Author(s)
      上田 顕
    • Organizer
      第1回 有機π電子系シンポジウム
    • Place of Presentation
      東京
    • Related Report
      2007 Annual Research Report
  • [Presentation] Bowl-Shaped π-Extended Semiquinone Radicals: Electronic Spin Structures of Ion Pairs with Alkaline-Metal Ions2007

    • Author(s)
      Ogasawara, K.
    • Organizer
      A Joint Conference of the International Symposium on Electron Spin Science and the 46th Annual Meeting of the Society of Electron Spin Science and Technology
    • Place of Presentation
      静岡市
    • Related Report
      2007 Annual Research Report
  • [Presentation] 曲面型の非交互π共役系における三次元的な分子内スピン間相互作用:コラヌレンを基盤とした安定中性ジラジカルの合成と性質2007

    • Author(s)
      上田 顕
    • Organizer
      第37回構造有機化学討論会
    • Place of Presentation
      札幌
    • Related Report
      2007 Annual Research Report
  • [Presentation] コラヌレンを基盤としたキレート配位部位を有する曲面型安定開殻有機分子の合成と電子スピン構造の解明2007

    • Author(s)
      小笠原華菜子
    • Organizer
      第37回構造有機化学討論会
    • Place of Presentation
      札幌
    • Related Report
      2007 Annual Research Report
  • [Presentation] 曲面π共役型安定中性ラジカル:三次元的な分子内スピン間相互作用の解明2007

    • Author(s)
      上田 顕
    • Organizer
      第1回分子科学討論会
    • Place of Presentation
      東北大学
    • Related Report
      2007 Annual Research Report
  • [Presentation] Intramolecular Spin-Spin Interaction through a Curved and non-Alternant Hydrocarbon: Corannulene with Phenoxyl Radical Moieties2007

    • Author(s)
      Ueda, A.
    • Organizer
      12th International Symposium on Novel Arom atic Compounds
    • Place of Presentation
      兵庫県立淡路夢舞台国際会議場
    • Related Report
      2007 Annual Research Report
  • [Presentation] Unique Spin-Delocalized Nature in Bowl-Shaped and Non-Alternan t π-Conjugated Systems: Syntheses and Characterization of Corannulene Derivatives Linked with a Stable Neutral Radical Moiety2007

    • Author(s)
      Ogasawara, K.
    • Organizer
      12th International Symposium on Novel Arom atic Compounds
    • Place of Presentation
      兵庫県立淡路夢舞台国際会議場
    • Related Report
      2007 Annual Research Report
  • [Presentation] 曲面型の非交互π共役骨格を基盤とした安定中性ラジカルの合成と電子スピン構造2007

    • Author(s)
      上田 顕
    • Organizer
      第91回有機合成シンポジウム
    • Place of Presentation
      東京工業大学
    • Related Report
      2007 Annual Research Report
  • [Patent(Industrial Property Rights)] 温度検知組成物およびその利用2007

    • Inventor(s)
      森田 靖、岡藤武治、山岸英雄
    • Industrial Property Rights Holder
      国立大学法人大阪大学、岡藤武治、株式会社カネカ
    • Industrial Property Number
      2007-303760
    • Filing Date
      2007-11-22
    • Related Report
      2007 Annual Research Report

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Published: 2006-04-01   Modified: 2016-04-21  

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