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安定高スピンπ電子系の創出と物性開拓

Publicly Offered Research

Project AreaEmergence of highly elaborated pai-space and its function
Project/Area Number 23108717
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionOsaka City University

Principal Investigator

鈴木 修一  大阪市立大学, 理学(系)研究科(研究院), 講師 (80433291)

Project Period (FY) 2011-04-01 – 2013-03-31
Project Status Completed (Fiscal Year 2012)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2012: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2011: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywords開殻π電子系 / 高スピン分子 / ラジカルカチオン
Outline of Annual Research Achievements

最近、開殻π電子系分子が、分子性磁石、光電導性、二次電池の活物質等の新たなエレクトロニクス材料として注目を浴びている。本研究者らは非常に大きな正の交換相互作用を有する三重項π電子系分子の合成・単離に成功してきた。これら開発した開殻π電子系を利用することで、スピン情報を制御したエレクトロニクス・スピントロニクス材料となると本研究者は考えている。本研究では、これまでの研究を発展した、(課題 1) 超強磁性的相互作用を持つ高スピンπ電子系の創成、(課題 2) 新規トリメチレンメタン型高スピンπ電子系の創成、(課題 3) 酸化還元による高スピンπ電子系の創成、の研究を行っている。本年度の成果を以下に示す。
課題 1 に関して、本研究者らが設計した異種ニトロキシド連結体の合成法を鍵として分子内の交換相互作用 J が +1000 K を有する安定な基底三重項分子の合成、単離、結晶化に成功した。
課題 2 に関して、ホウ素に二つまたは三つの電子豊富なπ電子系を導入した分子の合成に成功した。さらに、化学酸化することでラジカルカチオン種の合成に成功した。ジラジカルも発生には成功しなかったものの、ラジカルカチオンの性質に関する論文が Angew. Chem. Int. Ed. に掲載された。
課題 3 に関して、トリオキシトリフェニルアミンに三つのニトロキシドラジカルを導入した分子において、分子内の交換相互作用が、中性状態での反強磁性的、ラジカルカチオン状態で強磁性的となる新しいスピンスイッチ系の構築に成功した。また、ジヒドロフェナジンに二つのニトロニルニトロキシドラジカルを導入した系において、そのトリラジカルカチオン体の合成、単離、結晶化に成功した。

Research Progress Status

24年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

24年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2012 Annual Research Report
  • 2011 Annual Research Report
  • Research Products

    (50 results)

All 2013 2012 2011

All Journal Article (10 results) (of which Peer Reviewed: 10 results) Presentation (39 results) (of which Invited: 4 results) Book (1 results)

  • [Journal Article] Syntheses and Structural Studies of Tris(N-phenothiazinyl)borane and its Radical Cation2013

    • Author(s)
      S. Suzuki, K. Yoshida, M. Kozaki, K. Okada
    • Journal Title

      Angew. Chem.

      Volume: 52 Issue: 9 Pages: 2499-2502

    • DOI

      10.1002/anie.201208392

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] (Nitronyl Nitroxide)- substituted Trioxytriphenylamine Radical Cation Tetrachlorogallate Salt: A 2p Electron-Based Weak Ferromagnet Composed of Triplet Diradical Cation2012

    • Author(s)
      M. Kuratsu, S. Suzuki, M. Kozaki, D. Shiomi, K. Sato, T. Takui, T. Kanzawa, Y. Hosokoshi, X-Z. Lan, Y. Miyazaki, A. Inaba, K. Okada
    • Journal Title

      Chem. Asian. J.

      Volume: 7 Issue: 7 Pages: 1604-1609

    • DOI

      10.1002/asia.201200084

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chiral Stable Phenalenyl Radical: Synthesis, Electronic-spin Structure, and Optical Properties of [4]Helicene-structured Diazaphenalenyl2012

    • Author(s)
      Y. Morita, 他6人
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 51 Issue: 27 Pages: 6691-6695

    • DOI

      10.1002/anie.201202654

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Construction of Snowflake-Shaped Dendri- tic Covalent Assemblies with Rigid Conjugated Networks2012

    • Author(s)
      M. Kozaki, S. Morita, S. Suzuki, K. Okada
    • Journal Title

      J. Org. Chem.

      Volume: 77 Issue: 21 Pages: 9447-9457

    • DOI

      10.1021/jo3014512

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] NCN Pincer-Pt Complexes Coordinated by (Nitronyl Nitroxide)-2-ide Radical Anion2012

    • Author(s)
      X. Zhang, S. Suzuki, M. Kozaki, K. Okada
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 134 Issue: 43 Pages: 17866-17868

    • DOI

      10.1021/ja308103g

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Properties of Zn-porphyrin with Bipyridine-terminated Side Chains: Large Conformational Change Induced by Metal Complexation2012

    • Author(s)
      M. Kato, E. Hashimoto, M. Kozaki, S. Suzuki, K. Okada
    • Journal Title

      Tetrahedron Lett

      Volume: 53 Issue: 3 Pages: 309-312

    • DOI

      10.1016/j.tetlet.2011.11.041

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Trinitroxide-Trioxytriphenylamine : Spin-State Conversion from Triradical Doublet to Diradical Cation Triplet by Oxidative Modulation of a p-Conjugated System2012

    • Author(s)
      S.Suzuki
    • Journal Title

      Angew.Chem.Int.Ed.

      Volume: 51 Issue: 13 Pages: 3193-3197

    • DOI

      10.1002/anie.201107265

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Heteroatom Functionalization of Phenalenyl : Synthesis, Structures, and Properties of Hexa-substituted Phenalenyliums2011

    • Author(s)
      A.Ueda, K.Yoshida, S.Suzuki, K.Fukui, K.Nakasuji, Y.Morita
    • Journal Title

      Journal of Physical Organic Chemistry

      Volume: 24 Issue: 10 Pages: 952-959

    • DOI

      10.1002/poc.1916

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient Light-Harvesting Antenna with a Multi-Porphyrin Cascade2011

    • Author(s)
      A. Uetomo, M. Kozaki, S. Suzuki, K. Yamanaka, O. Ito, K. Okada
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 133 Issue: 34 Pages: 13276-13279

    • DOI

      10.1021/ja2050343

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Recent Progress in Controlling Photophysical Processes of Donor-Acceptor Arrays Involving Perylene Diimides and Boron-dipyrromethenes2011

    • Author(s)
      S. Suzuki, M. Kozaki, K. Nozaki, K. Okada
    • Journal Title

      J. Photochem. Photobiol. C: Photocemistry Reviews

      Volume: 12 Issue: 4 Pages: 269-292

    • DOI

      10.1016/j.jphotochemrev.2011.10.001

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Presentation] Syntheses and Properties of Organic High-spin Molecular Systems Based on Nitronyl Nitroxide Radical2013

    • Author(s)
      鈴木修一
    • Organizer
      日本化学会第 93 春季年会 アジア国際シンポジウム
    • Place of Presentation
      立命館大学びわこ・くさつキャンパス
    • Year and Date
      2013-03-22
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] ニトロキシドラジカルを基盤とする安定高スピンπ電子系の創出2013

    • Author(s)
      鈴木修一
    • Organizer
      新学術領域研究「高次π空間の創発と機能開発」第 9 回公開シンポジウム
    • Place of Presentation
      神戸
    • Year and Date
      2013-03-13
    • Related Report
      2012 Annual Research Report
  • [Presentation] スピン状態制御を指向したπ電子系分子の設計と合成2012

    • Author(s)
      鈴木修一
    • Organizer
      第 6 回有機π電子系シンポジウム
    • Place of Presentation
      松山・愛媛
    • Year and Date
      2012-12-14
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Spin-switching Properties of Electron Donor Molecules Substituted with Stable Neutral Radicals2012

    • Author(s)
      鈴木修一
    • Organizer
      新学術領域研究「高次π空間の創発と機能開発」第 4 回国際シンポジウム
    • Place of Presentation
      Hamamatsu, Shizuoka
    • Year and Date
      2012-11-13
    • Related Report
      2012 Annual Research Report
  • [Presentation] Syntheses and Magnetic Properties of Nitronyl-Nitroxides with an Adjacent Chiral Group2012

    • Author(s)
      鈴木修一
    • Organizer
      The 13th International Conference on Molecule-based Magnets
    • Place of Presentation
      Florida, USA
    • Year and Date
      2012-10-07
    • Related Report
      2012 Annual Research Report
  • [Presentation] Syntheses and Magnetic Properties of Stable-radicals-substituted π-Donor Molecules2012

    • Author(s)
      鈴木修一
    • Organizer
      The 13th International Conference on Molecule-based Magnets
    • Place of Presentation
      Florida, USA
    • Year and Date
      2012-10-07
    • Related Report
      2012 Annual Research Report
  • [Presentation] Synthesis and Redox Properties of Nitronyl Nitroxide-Pt Pincer-Type Complexes2012

    • Author(s)
      鈴木修一
    • Organizer
      The 13th International Conference on Molecule-based Magnets
    • Place of Presentation
      Florida, USA
    • Year and Date
      2012-10-07
    • Related Report
      2012 Annual Research Report
  • [Presentation] Synthesis and Structure of Palladium Complexes Coordinated by Nitronyl Nitroxides2012

    • Author(s)
      鈴木修一
    • Organizer
      The 13th International Conference on Molecule-based Magnets
    • Place of Presentation
      Florida, USA
    • Year and Date
      2012-10-07
    • Related Report
      2012 Annual Research Report
  • [Presentation] ニトロニルニトロキシド-アミジン誘導体とその金属錯体の合成と物性2012

    • Author(s)
      鈴木修一
    • Organizer
      錯体化学会第 62 回討論会
    • Place of Presentation
      富山大学
    • Year and Date
      2012-09-21
    • Related Report
      2012 Annual Research Report
  • [Presentation] ニトロニルニトロキシドが直接置換した金属錯体の合成と電気化学的性質2012

    • Author(s)
      鈴木修一
    • Organizer
      錯体化学会第 62 回討論会
    • Place of Presentation
      富山大学
    • Year and Date
      2012-09-21
    • Related Report
      2012 Annual Research Report
  • [Presentation] 二つのニトロニルニトロキシドラジカルアニオンが直接配位したパラジウム錯体の合成と性質2012

    • Author(s)
      鈴木修一
    • Organizer
      第 23 回基礎有機化学討論会
    • Place of Presentation
      京都テルサ・京都
    • Year and Date
      2012-09-19
    • Related Report
      2012 Annual Research Report
  • [Presentation] トリオキシトリフェニルアミンの一電子および二電子酸化体の合成と構造2012

    • Author(s)
      鈴木修一
    • Organizer
      第 23 回基礎有機化学討論会
    • Place of Presentation
      京都テルサ・京都
    • Year and Date
      2012-09-19
    • Related Report
      2012 Annual Research Report
  • [Presentation] Syntheses and Structures of Triphenothiazinylborane and its Analogues in Neutral and Cationic States2012

    • Author(s)
      鈴木修一
    • Organizer
      The 6th Russian-Japanese Workshop on Open Shell Compounds and Molecular Spin Devices
    • Place of Presentation
      Rostov-on-Don, Russia
    • Year and Date
      2012-09-09
    • Related Report
      2012 Annual Research Report
  • [Presentation] 開殻π電子系導入型金属錯体:ラジカル直結白金錯体の合成研究2012

    • Author(s)
      鈴木修一
    • Organizer
      新学術領域研究「高次π空間の創発と機能開発」第 8 回公開シンポジウム
    • Place of Presentation
      慶応大学・神奈川
    • Year and Date
      2012-07-23
    • Related Report
      2012 Annual Research Report
  • [Presentation] Structures and Redox Properties of Triphenothiazinylborane and Their Analogues2012

    • Author(s)
      鈴木修一
    • Organizer
      The 10th International Conference on Heteroatom Chemistry
    • Place of Presentation
      京都大学宇治キャンパス
    • Year and Date
      2012-05-20
    • Related Report
      2012 Annual Research Report
  • [Presentation] Syntheses and Properties of Metal Complexes Directly Linked to Nitronyl Nitroxide2012

    • Author(s)
      鈴木修一
    • Organizer
      International Workshop on Open-shell Molecular Systems
    • Place of Presentation
      Osaka University, Osaka
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] 白金とスピンを鍵とする新規錯体の合成と物性2012

    • Author(s)
      鈴木修一
    • Organizer
      第 47 回錯体化学若手の会
    • Place of Presentation
      神戸・兵庫
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] ビス(フェノチアジニル)ボランアミン類縁体の合成と性質2012

    • Author(s)
      鈴木修一, 他
    • Organizer
      新学術領域研究「高次π空間の創発と機能開発」第7回公開シンポジウム
    • Place of Presentation
      メルパルク松山・愛媛
    • Related Report
      2011 Annual Research Report
  • [Presentation] キラル中心直結型ニトロニルニトロキシド誘導体の合成と物性2012

    • Author(s)
      谷本理勇, 他
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応大学日吉・矢上キャンパス・神奈川
    • Related Report
      2011 Annual Research Report
  • [Presentation] ニトロニルニトロキシドラジカルのC2アニオン配位型金属錯体の合成2012

    • Author(s)
      横井宙是, 他
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応大学日吉・矢上キャンパス・神奈川
    • Related Report
      2011 Annual Research Report
  • [Presentation] ビス(フェノチアジニル)ボランアミンおよび類縁体:中性種および酸化体の合成と構造2012

    • Author(s)
      吉田考平, 他
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応大学日吉・矢上キャンパス・神奈川
    • Related Report
      2011 Annual Research Report
  • [Presentation] ニトロニルニトロキシドが直接連結した単核および二核白金錯体の合成と性質2012

    • Author(s)
      張〓, 他
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応大学日吉・矢上キャンパス・神奈川
    • Related Report
      2011 Annual Research Report
  • [Presentation] 安定な開殼π電子系集積分子の合成と物性解明2012

    • Author(s)
      鈴木修一, 他
    • Organizer
      日本化学会第92春季年会
    • Place of Presentation
      慶応大学日吉・矢上キャンパス・神奈川(招待講演)
    • Related Report
      2011 Annual Research Report
  • [Presentation] Redox Switching Properties of Trinitroxide-Substituted Trioxytriphenylamine2011

    • Author(s)
      鈴木修一
    • Organizer
      The 16th Osaka City University International Symposium on Dynamic Molecular Devices
    • Place of Presentation
      大阪市立大学・大阪(招待講演)
    • Year and Date
      2011-11-09
    • Related Report
      2011 Annual Research Report
  • [Presentation] 安定高スピンπ電子系の創出と物性開拓2011

    • Author(s)
      鈴木修一
    • Organizer
      新学術領域研究「高次π空間の創発と機能開発」第6回公開シンポジウム
    • Place of Presentation
      岡崎コンファレンスセンター・愛知
    • Related Report
      2011 Annual Research Report
  • [Presentation] 安定中性ラジカル導入型白金錯体の合成と構造2011

    • Author(s)
      張〓, 他
    • Organizer
      錯体化学会第61回討論会
    • Place of Presentation
      岡山理科大学・岡山
    • Related Report
      2011 Annual Research Report
  • [Presentation] ビス(ニトロニルニトロキシド)置換ジヒドロフェナジンラジカルカチオンの合成と磁気的性質2011

    • Author(s)
      永田充輝, 他
    • Organizer
      第22回基礎有機化学討論会
    • Place of Presentation
      つくば国際会議場・茨城
    • Related Report
      2011 Annual Research Report
  • [Presentation] (ジアリールアミノ)ボラン中性種および酸化体の合成と性質2011

    • Author(s)
      吉田考平, 他
    • Organizer
      第22回基礎有機化学討論会
    • Place of Presentation
      つくば国際会議場・茨城
    • Related Report
      2011 Annual Research Report
  • [Presentation] Spin-state Switching Property of Trinitroxide-trioxytriphenylamine from Triradical Doublet to Diradical Cation Triplet2011

    • Author(s)
      鈴木修一, 他
    • Organizer
      MDF International Workshop : Open-shell Organic Molecules ; Synthesis and Electronic Structure Freedom
    • Place of Presentation
      梅田スカイビル・大阪(招待講演)
    • Related Report
      2011 Annual Research Report
  • [Presentation] Properties of (Nitronyl Nitroxide)-(Pincer-type Platinum Complex) Dyad2011

    • Author(s)
      張〓, 他
    • Organizer
      MDF International Workshop : Open-shell Organic Molecules ; Synthesis and Electronic Structure Freedom
    • Place of Presentation
      梅田スカイビル・大阪
    • Related Report
      2011 Annual Research Report
  • [Presentation] High-spin Ground State Triradical Cation : Synthesis and Properties of Bis(Nitronyl-nitroxides)-substituted Dihydrophenazine2011

    • Author(s)
      永田充輝, 他
    • Organizer
      MDF International Workshop : Open-shell Organic Molecules ; Synthesis and Electronic Structure Freedom
    • Place of Presentation
      梅田スカイビル・大阪
    • Related Report
      2011 Annual Research Report
  • [Presentation] Structures and Properties of Triphenothiazinylborane and its Radical Cation2011

    • Author(s)
      吉田考平, 他
    • Organizer
      MDF International Workshop : Open-shell Organic Molecules ; Synthesis and Electronic Structure Freedom
    • Place of Presentation
      梅田スカイビル・大阪
    • Related Report
      2011 Annual Research Report
  • [Presentation] Stable Bisnitroxides with Large Exchange Interactions2011

    • Author(s)
      岡田惠次
    • Organizer
      The Fifth Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
    • Place of Presentation
      淡路夢舞台国際会議場・兵庫
    • Related Report
      2011 Annual Research Report
  • [Presentation] Trinitroxide-trioxytriphenylamine : Redox and Magnetic Properties in Neutral and Cationic States2011

    • Author(s)
      鈴木修一
    • Organizer
      The Fifth Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
    • Place of Presentation
      淡路夢舞台国際会議場・兵庫
    • Related Report
      2011 Annual Research Report
  • [Presentation] Synthesis of Bis(nitronyl-nitroxides)-substituted Dihydrophenazine Radical Cation with Quartet Ground State2011

    • Author(s)
      永田充輝
    • Organizer
      The Fifth Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
    • Place of Presentation
      淡路夢舞台国際会議場・兵庫
    • Related Report
      2011 Annual Research Report
  • [Presentation] Triphenothiazinylborane : Syntheses, Structures, and Redox Properties2011

    • Author(s)
      吉田考平
    • Organizer
      The Fifth Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
    • Place of Presentation
      淡路夢舞台国際会議場・兵庫
    • Related Report
      2011 Annual Research Report
  • [Presentation] Syntheses and Redox Properties of Pincer-Type Platinum Complex Directly Linked to Nitronyl Nitroxide2011

    • Author(s)
      張〓
    • Organizer
      The Fifth Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
    • Place of Presentation
      淡路夢舞台国際会議場・兵庫
    • Related Report
      2011 Annual Research Report
  • [Presentation] Synthetic Studies on Stable High-spin p-Electronic Compounds with Large Intramolecular Exchange Interactions2011

    • Author(s)
      鈴木修一, 他
    • Organizer
      新学術領域研究「高次π空間の創発と機能開発」第4回若手研究会
    • Place of Presentation
      物質・材料研究機構千現地区・茨城
    • Related Report
      2011 Annual Research Report
  • [Presentation] Stable Open-shell pi-Electronic System : Magnetic Properties of Trinitroxide-trioxytriphenylamine in Neutral and Cationic States2011

    • Author(s)
      鈴木修一, 他
    • Organizer
      新学術領域研究「高次π空間の創発と機能開発」第3回国際シンポジウム
    • Place of Presentation
      つくば国際会議場・茨城
    • Related Report
      2011 Annual Research Report
  • [Book] 高次π空間の創発と機能開発2013

    • Author(s)
      赤坂 健(編)
    • Total Pages
      245
    • Publisher
      シーエムシー出版
    • Related Report
      2012 Annual Research Report

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Published: 2011-04-06   Modified: 2018-03-28  

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