Syntheses of organic radicals having electronic-spin structures corresponding to outer environmental atmosphere

• Project/Area Number: 19350022
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: MORITA Yasushi Osaka University, 大学院・理学研究科, 准教授 (70230133)
• Project Period (FY): 2007 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥20,410,000 (Direct Cost: ¥15,700,000、Indirect Cost: ¥4,710,000); Fiscal Year 2008: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000); Fiscal Year 2007: ¥14,690,000 (Direct Cost: ¥11,300,000、Indirect Cost: ¥3,390,000)
• Keywords: 開殻分子 / フェナレニル / オキソフェナレノキシル / 電子スピン / 非局在性 / 電子移動 / ソルバトクロミズム / サーモクロミズム / 奇交互炭化水素

Research Abstract

分子骨格全体に広く非局在化した電子スピンを有し空気中でも安定な中性ラジカルである6-オキソフェナレノキシルに着目し、電子供与性分子や相補的水素結合が可能な核酸塩基類等を結合させた中性ラジカルを合成した。そして、溶液状態における溶媒や温度変化、光照射などに応答した分子内電子移動の動的な挙動や、電子スピンの非局在化様式を明らかにした。

Research Products

• [Journal Article] Hydrogen-Bond Interaction in OrganicConductors : Redox Activation, MolecularRecognition, Structural Regulation, andProton-Transfer in Donor-AcceptorCharge-Transfer Complexes of TTF-Imidazole (2009)
  • Author(s): Murata, T. ; Morita, Y. ; Yakiyama, Y. ; Fukui, K. ;Yamochi, H. ; Saito, G. ; Nakasuji, K.
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 10837-10846
  • Peer Reviewed
• [Journal Article] Curve-Structured Phenalenyl Chemistry : Synthesis, Electronic Structure, and Bowl-Inversion Barrier of a Phenalenyl-Fused Corannulene Anion (2008)
  • Author(s): Nishida, S. ; Morita, Y. ; Ueda, A. ; Kobayashi, T. ; Fukui, K. ; Ogasawara, K. ; Sato, K. ; Takui, T. ; Nakasuji, K.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 14954-14955
  • Peer Reviewed
• [Journal Article] Oxophenalenoxyl : Novel Stable Neutral Radical with a Unique Spin-Delocalized Nature Depending on Topological Symmetries and Redox State (2008)
  • Author(s): Morita, Y. ; Nishida, S. ; Kawai, J. ; Takui, T. ; Nakasuji, K.
  • Journal Title: Pure Appl. Chem. 80 Pages: 507-517
  • Peer Reviewed
• [Journal Article] Curved Aromaticity of a Corannulene-Based Neutral Radical : Crystal Structure and 3D Unbalanced Delocalization of Spin (2008)
  • Author(s): Morita, Y. ; Ueda, A. ; Nishida, S. ; Fukui, K. ; Ise, T. ; Shiomi, D. ; Sato, K. ; Takui, T. ; Nakasuji, K.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 2035-2038
  • Peer Reviewed
• [Journal Article] Thermochromism in an Organic CrystalBased on the Co-existence of σ-and π-Dimers (2008)
  • Author(s): Morita, Y. ; Suzuki, S. ; Fukui, K. ; Nakazawa, S. ; Kitagawa, H. ; Kishida, H. ; Okamoto, H. ; Naito, A. ; Sekine, A. ; Ohashi, Y. ; Shiro, M. ; Sasaki, K. ; Shiomi, D. ; Sato, K. ; Takui, T. ; Nakasuji, K.
  • Journal Title: Nature Mater 7 Pages: 48-51
  • Peer Reviewed
• [Journal Article] Curve-Structured Phenalenyl Chemistry : Synthesis, Electronic Structure, and Bowl-Inversion Barrier of a Phenalenyl-Fused Corannulene Anion (2008)
  • Author(s): Nishida, S.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 14954-14955
  • Peer Reviewed
• [Journal Article] Synthesis, Crystal Structure, and Properties of a New Hydrogen-bonded Electron-donor : 1, 6-Dithiapyrene-imidazole (2008)
  • Author(s): Morita, Y.
  • Journal Title: Solid State Sci. 10 Pages: 1720-1723
  • Peer Reviewed
• [Journal Article] Hydrogen-Bond Architectures of Protonated 4, 4-Biimidazolium Derivatives and Oligo(imidazolium)s in Charge-Transfer Salts with Tetracyanoquinodimethane (2008)
  • Author(s): Murata, T.
  • Journal Title: Crvst. Growth Des. 8 Pages: 3058-3065
  • Peer Reviewed
• [Journal Article] Macrocyclic High-Spin (S=2)Molecule : Spin Identification of A Sterically Rigid Metacyclophane-Based Nitroxide Tetraradical by Two-Dimensional Electron Spin Transient Nutation Spectroscopy (2008)
  • Author(s): Sawai, T.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 3988-3990
  • Peer Reviewed
• [Journal Article] Oxophenalenoxyl : Novel Stable Neutral Radical with a Unique Spin-Delocalized Nature Depending on Topological Symmetries and Redox State (2008)
  • Author(s): Morita, Y.
  • Journal Title: Pure Appl. Chem. 80 Pages: 507-517
  • Peer Reviewed
• [Journal Article] 空気中でも安定に取り扱うことができる有機中性ラジカル : スピン非局在型の電子スピン構造と動的な電子スピン物性の創成 (2008)
  • Author(s): 森田靖
  • Journal Title: 機能材料 28 Pages: 13-20
• [Journal Article] 分子スピン量子コンピュータ/量子情報処理システムの開発 (2008)
  • Author(s): 北川勝浩
  • Journal Title: 化学と工業 62 Pages: 31-33
• [Journal Article] Curved Aromaticity of a Corannulene-Based Neutral Radical: Crystal Structure and 3D Unbalanced Delocalization of Spin (2008)
  • Author(s): Morita, Y.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 2035-2038
  • Peer Reviewed
• [Journal Article] A Novel TTF-based Electron-donor with Imidazole-annelation Having Hvdrogen-bond and Proton-transfer Abilities (2008)
  • Author(s): Morita, Y.
  • Journal Title: Chem. Lett. 37 Pages: 24-25
  • Peer Reviewed
• [Journal Article] Thermochromism in an Organic Crystal Based on the Co-existence of σ-and π-Dimers (2008)
  • Author(s): Morita, Y.
  • Journal Title: Nature Mater. 7 Pages: 48-51
  • Peer Reviewed
• [Journal Article] Implementation of Molecular Spin Quantum Computing by Pulsed ENDOR Technique: Direct Observation of Quantum Entanglement and Spinor (2007)
  • Author(s): Sato, K.
  • Journal Title: Physica E: Low-dimensional Systems and Nanostructures 40 Pages: 363-366
  • Peer Reviewed
• [Journal Article] Syntheses and Characterizations of Acetylene-Linked Bisphenalenyl and Metallic-like Behavior in Its Charge-Transfer Complex (2007)
  • Author(s): Kubo, T.
  • Journal Title: Chem. Asian J. 2 Pages: 1370-1379
  • Peer Reviewed
• [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.
  • Journal Title: J. Phys. Chem. A 111 Pages: 9102-9110
  • 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 Interaction (2007)
  • Author(s): Murata, T.
  • Journal Title: Chem. Commun. Pages: 4009-4011
  • Peer Reviewed
• [Journal Article] Ambipolar Organic Field-effect Transistors Based on a Low Band Gap Semiconductor with Balanced Hole and Electron Mobilities (2007)
  • Author(s): Chikamatsu, M.
  • Journal Title: Appl. Phys. Lett. 91
  • 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-Imidazole (2007)
  • Author(s): Murata, T.
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 10837-10846
  • Peer Reviewed
• [Journal Article] TTF-Cytosine Dyad as an Electron-donor Molecule Having Proton-accepting Ability: Formation of Hemiprotonated Cytosine Dimer in I_3-Salt (2007)
  • Author(s): Miyazaki, E.
  • Journal Title: Chem. Lett. 36 Pages: 1102-1103
  • 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 Calculations (2007)
  • Author(s): Nishida, S.
  • Journal Title: Tetrahedron 63 Pages: 7690-7695
  • Peer Reviewed
• [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.
  • Journal Title: J. Phys. Chem. A 111 Pages: 3633-3641
  • Peer Reviewed
• [Presentation] π電子拡張型フェナレニルラジカルの新た展開 (2009)
  • Author(s): 森田靖
  • Organizer: シングレットビラジカルの化学と展望
  • Place of Presentation: 分子科学研究所
• [Presentation] Material Challenges for Air-stable Neutral Radicals with Polynuclear Benzenoid Structures (2009)
  • Author(s): Morita, Y.
  • Organizer: Okazaki Conference : From Aromatic Molecules to Graphene : Chemistry, Physics and Device Applications
  • Place of Presentation: 分子科学研究所
• [Presentation] 電子ドナーを置換した6-オキソフェナレノキシル安定中性ラジカルのスピン中心移動とクロミズム (2008)
  • Author(s): 山中あずさ
  • Organizer: 第6回京都大学福井謙一記念研究センターシンポジウム
  • Place of Presentation: 京都
  • Year and Date: 2008-12-02
• [Presentation] Air-stable Organic Neutral Radicals : From Dynamic Electronic-spin Natures to Chemical Batteries (2008)
  • Author(s): Morita, Y.
  • Organizer: International Symposium on Molecular Conductors (ISMC2008)
  • Place of Presentation: 分子科学研究所
• [Presentation] 有機π電子系への電子スピンや水素結合能の導入 : 分子間相互作用の制御に基づく特異な動的電子物性の創出 (2008)
  • Author(s): 森田靖
  • Organizer: 第2回有機π電子系シンポジウム
  • Place of Presentation: 広島
• [Presentation] 外部環境の変化に伴いさまざまに色を変えるカメレオンラジカル (2008)
  • Author(s): 山中あずさ
  • Organizer: 第2回有機π電子系シンポジウム
  • Place of Presentation: 広島
• [Presentation] Spin-Center Transfer of 1, 6-Dithiapyrene-incorporated 6-Oxophen alenoxyl : Electronic-spin Structure of Neutral and Zwitterionic Radical States Determined by ENDOR/TRIPLE Spectroscopies (2008)
  • Author(s): Yamanaka, A.
  • Organizer: IV International Conference “High-spin Molecules and Molecular Magnets"
  • Place of Presentation: ロシア
• [Presentation] スピン中心移動 : 1H-ENDOR/TRIPLE法によるDTPY置換6-オキソフェナレノキシルの電子スピン構造の解明 (2008)
  • Author(s): 山中あずさ
  • Organizer: 第19回基礎有機化学討論会
  • Place of Presentation: 大阪
• [Presentation] Air-stable Organic Neutral Radicals : From Dynamic Electronic-spin Natures to Chemical Batteries (2008)
  • Author(s): Y. Morita
  • Organizer: International Symposium on Molecular Conductors
  • Place of Presentation: 愛知
• [Presentation] Redox-Based Spin Diversity: 6-オキソフェナレノキシルを基盤とした中性ジラジカルのレドックスに応答したスピン間相互作用 (2008)
  • Author(s): 西田辰介
  • Organizer: 日本化学会第88季年会
  • Place of Presentation: 東京
• [Presentation] 核酸塩基を導入した6-オキソフェナレノキシル型安定中性ラジカルの合成と性質 (2008)
  • Author(s): 山中あずさ
  • Organizer: 日本化学会第88季年会
  • Place of Presentation: 東京
• [Presentation] A New Trend in Purely Organic Open-shell Molecules : π-Extensions and Multi-step Redox Abilities of Phenalenyl Systems (2007)
  • Author(s): Morita, Y.
  • Organizer: 12th International Symposium on Novel Aromatic Compounds (ISNA-12)
  • Place of Presentation: 兵庫県立淡路夢舞台国際会議場
• [Presentation] Novel Homo-Spin Diradical System Based on 6-Oxophenalenoxyl Stable Neutral Radical: Electronic Spin Structure and Multi-Step Redox Ability (2007)
  • Author(s): Nishida, S.
  • 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
• [Presentation] 多重水素結合部位を有する核酸塩基を導入した6-オキソフェナレノキシル誘導体の合成と性質 (2007)
  • Author(s): 山中あずさ
  • Organizer: 第37回構造有機化学討論会
  • Place of Presentation: 札幌
• [Presentation] Molecular Crystalline Secondary Battery: Multi-Electron Chargeable Ability Correlated with Redox Properties of 6-Oxophenalenoxyl-B ased Neutral Radicals (2007)
  • Author(s): Nishida, S.
  • Organizer: Seventh International Symposium On Crystalline Organic Metals, Superconductors And Ferromagnets
  • Place of Presentation: スペイン
• [Presentation] Hydrogen-Bond Interactions in Organic pi-Electronic Systems: Molecular Recognition, Structural Regulation, and Redox Activation (2007)
  • Author(s): Morita, Y.
  • Organizer: Post-symposium in Himeji on Functional Aromatic Compounds
  • Place of Presentation: 姫路
• [Presentation] A New Trend in Purely Organic Open-shell Molecules: π-Extensions and Multi-step Redox Abilities of Phenalenyl Systems (2007)
  • Author(s): Morita, Y.
  • Organizer: 12th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: 兵庫県立淡路夢舞台国際会議場
• [Presentation] Temperature-Dependent Redox Potentials of 6-Oxophenalenoxyl Neutral Radicals Linked with Electron Donor Moiety: Low Temperature CV Studies (2007)
  • Author(s): Nishida, S.
  • Organizer: 12th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: 兵庫県立淡路夢舞台国際会議場
• [Book] 機能材料(シーエムシー出版) (2008)
  • Author(s): 森田靖
  • Publisher: 空気中でも安定に取り扱うことができる有機中性ラジカル : スピン非局在型の電子スピン構造と動的な電子スピン物性の創成
• [Remarks] 新聞報道 : 「有機分子結晶温度で濃淡変化阪大・大阪市立大開発」,日本経済新聞2007年11月26日(月)朝刊12版19面ホームページ
  • URL: http://www.chem.sci.osaka-u.ac.jp/lab/nakasuji/
• [Patent(Industrial Property Rights)] 有機半導体素子 (2008)
  • Inventor(s): 森田 靖, 横山正明, 柳田祥三, 太和田善久, 山本憲治, 辻 良太郎
  • Industrial Property Rights Holder: 国立大学法人大阪大学, 株式会社カネカ
  • Industrial Property Number: 2008-302912
  • Filing Date: 2008-11-27
• [Patent(Industrial Property Rights)] 電極活物質、及び二次電池 (2008)
  • Inventor(s): 森田 靖, 西田辰介, 工位武治, 佐藤正春, 芥川奈緒
  • Industrial Property Rights Holder: 国立大学法人大阪大学, 公立大学法人大阪市立大学, 株式会社村田製作所
  • Industrial Property Number: 2008-249050
  • Filing Date: 2008-09-26
• [Patent(Industrial Property Rights)] 電極活物質、及び二次電池 (2008)
  • Inventor(s): 森田 靖, 西田辰介, 工位武治, 佐藤正春, 芥川奈緒
  • Industrial Property Rights Holder: 国立大学法人大阪大学, 公立大学法人大阪市立大学, 株式会社村田製作所
  • Industrial Property Number: 2008-219401
  • Filing Date: 2008-08-28
• [Patent(Industrial Property Rights)] 電極活物質、及び二次電池 (2008)
  • Inventor(s): 森田 靖, 西田辰介, 工位武治, 佐藤正春, 芥川奈緒
  • Industrial Property Rights Holder: 国立大学法人大阪大学, 公立大学法人大阪市立大学, 株式会社村田製作所
  • Filing Date: 2008-08-08
• [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
  • Filing Date: 2007-11-22
• [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