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ランタノイド-フタロシアニン系単分子磁石の多重機能化

Research Project

Project/Area Number 13J02441
Research Category

Grant-in-Aid for JSPS Fellows

Allocation TypeSingle-year Grants
Section国内
Research Field Functional materials/Devices
Research InstitutionTohoku University

Principal Investigator

守田 峻海  東北大学, 理学研究科, 特別研究員(DC1)

Project Period (FY) 2013-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2015: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2014: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2013: ¥900,000 (Direct Cost: ¥900,000)
Keywords単分子磁石 / ランタノイド / フタロシアニン / 常磁性種の核磁気共鳴 / 磁化率異方性テンソル / 磁化緩和 / 磁気双極子相互作用 / 交換バイアス / 磁気ヒステリシス
Outline of Annual Research Achievements

本研究では、化学的に安定でスピン反転のエネルギー障壁が大きい、ランタノイド-フタロシアニン系単分子磁石に注目して研究を行っている。これまでに合成された様々なランタノイド(III)-フタロシアニン単分子磁石のNMRスペクトルから、本系における常磁性シフトの解析が確立されつつある。本系の常磁性シフトは、観測核とランタノイドイオンの相対位置(Gパラメーター)に大きく依存する擬コンタクトシフトが支配的である。すなわち、シグナルが正しく帰属できると、常磁性シフトの値と分子の構造から、磁化率異方性テンソルの成分を計算することができる。本研究では、テルビウム(III)-フタロシアニントリプルデッカー、テルビウム(III)-縮環フタロシアニントリプルデッカー型錯体の、二つの単分子磁石の磁化率異方性テンソルのアキシャル成分を比較した。同テンソルのアキシャル成分とスピン反転のエネルギー障壁の起源はランタノイドイオンの配位子場分裂によるものであるから、同テンソルのアキシャル成分は単分子磁石の一軸異方性の度合いを示す指標となり得る。この二つの単分子磁石には、同じGパラメーターを持ったプロトンがそれぞれ存在している。つまり、これらのプロトンの常磁性シフトを比較した場合、その度合いは分子の一軸性にのみに依存するということである。実際の化学シフトの値を比べると、縮環フタロシアニントリプルデッカーのプロトン方がより負の方向にシフトしていた。これは、この錯体の一軸磁気異方性がフタロシアニントリプルデッカーよりも大きいことを示している。つまり、この差は両者の一軸異方性の度合い、即ち、単分子磁石特性の差異を示していると考えられる。これは、単分子磁石特性を、室温付近の測定で評価できたことを示している。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Report

(3 results)
  • 2015 Annual Research Report
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • Research Products

    (22 results)

All 2015 2014 2013

All Journal Article (4 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 4 results,  Acknowledgement Compliant: 2 results) Presentation (18 results) (of which Int'l Joint Research: 3 results)

  • [Journal Article] Alpha-Substituted Bis(octabutoxyphthalocyaninato)Terbium(III): Preparation and Study of Protonation by NMR and DFT2015

    • Author(s)
      M. Damjanovic, Y. Horie, T. Morita, Y. Horii, K. Katoh, M. Yamashita, M. Enders
    • Journal Title

      Inorg. chem.

      Volume: 54 Issue: 24 Pages: 11986-11992

    • DOI

      10.1021/acs.inorgchem.5b02391

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Ligand π-Radical Interaction with f-shel Unpaired Electrons in Phthalocyaninato-Lanthanoid Single-Molecule Magnets; A Solution NMR Spectroscopic and DFT Study2015

    • Author(s)
      M. Damjanovic, T. Morita, K. Katoh, M. Yamashita, M. Enders
    • Journal Title

      Chem. Eur. J.

      Volume: 21 Issue: 41 Pages: 7096-7102

    • DOI

      10.1002/chem.201501944

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Effect off-f Interactions on Quantum Tunneling of the Magnetization : Mono-and Dinuclear Dy (III) Phthalocyaninato Triple-Decker Single-Molecule Magnets with the Same Octacoordination Enviroment2014

    • Author(s)
      Keiichi Katoh, Rina Asano, Akira Miura, Yoji Horii, Takaumi Morita, Brian K. Breedlove, Masahiro Yamashita
    • Journal Title

      Dalton Transactions

      Volume: (印刷中)(掲載確定)

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Controlling the Dipole-Dipole Interactions between Terbium (III) Phthalocy aninato Triple-Decker Moieties through Spatial Control Using a Fused Ph thalocyaninato Ligand2013

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Journal Title

      Inorganic Chemistry

      Volume: 52 Issue: 23 Pages: 13555-13561

    • DOI

      10.1021/ic4020459

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Presentation] テルビウム(III)-縮環フタロシアニン単分子磁石の構造と磁気特性2015

    • Author(s)
      守田 峻海, Marko Damjanovic, 加藤 恵一, Brian K. Breedlove, 高石 慎也, Markus Enders, 山下 正廣
    • Organizer
      第65回錯体化学討論会
    • Place of Presentation
      奈良
    • Year and Date
      2015-09-21
    • Related Report
      2015 Annual Research Report
  • [Presentation] テルビウム(III)-フタロシアニン単分子磁石のNMR測定における常磁性シフトの解析2015

    • Author(s)
      守田 峻海, Marko Damjanovic, 加藤 恵一, Markus Enders, 山下 正廣
    • Organizer
      第9回分子科学討論会
    • Place of Presentation
      東京
    • Year and Date
      2015-09-16
    • Related Report
      2015 Annual Research Report
  • [Presentation] NMR Analysis of Terbium(III)-Phthalocyaninato Single Molecule Magnet2015

    • Author(s)
      Marko Damjanovic, Takaumi Morita, Keiichi Katoh, Masahiro Yamashita, Markus Enders
    • Organizer
      Tohoku University’s Chemistry Summer School 2015
    • Place of Presentation
      Sendai, Miyagi, Japan
    • Year and Date
      2015-08-25
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Single-Molecule Magnet Properties of a Tetranuclear Dy(III)-Fused Phthalocyaninato Quintuple-Decker Complex2015

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      Tohoku University’s Chemistry Summer School 2015
    • Place of Presentation
      Sendai, Miyagi, Japan
    • Year and Date
      2015-08-25
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Single-Molecule Magnet Properties of a Tetranuclear Dy(III)-Fused Phthalocyaninato Quintuple-Decker Complex2015

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      5th Asian Conference on Coordination Chemistry
    • Place of Presentation
      Hong Kong
    • Year and Date
      2015-07-12
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] NMR Analysis of Terbium(III)-Phthalocyaninato Single Molecule Magnets2015

    • Author(s)
      Marko Damjanovic, Takaumi Morita, Keiichi Katoh, Masahiro Yamashita and Markus Enders
    • Organizer
      Heidelberg Forum of Molecular Catalysis 2015
    • Place of Presentation
      Heidelberg, Germany
    • Year and Date
      2015-06-12
    • Related Report
      2015 Annual Research Report
  • [Presentation] 遅い磁化緩和挙動を示すテルビウム(III)-縮環フタロシアニン積層型錯体の合成2015

    • Author(s)
      守田 峻海, 加藤 恵一, 高石 慎也, Brian K. Breedlove, 山下 正廣
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学 船橋キャンパス
    • Year and Date
      2015-03-26 – 2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] Highest Reported Temperature for Hysteresis of the Magnetization of a Single-Molecule Magnet2014

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      The 16th Japan-Korea Joint Symposium on Organometallic and Coordination Chemistry
    • Place of Presentation
      東北大学 片平キャンパス さくらホール
    • Year and Date
      2014-10-24 – 2014-10-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] Highest Reported Temperature for Hysteresis of the Magnetization of a Single-Molecule Magnet2014

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      5th International Conference of Organic Semiconductors
    • Place of Presentation
      Egret Himeji, 姫路
    • Year and Date
      2014-10-13 – 2014-10-17
    • Related Report
      2014 Annual Research Report
  • [Presentation] テルビウム(III)-フタロシアニン積層型錯体のNMRを用いた構造解析2014

    • Author(s)
      守田 峻海, Marko Damjanovic, 加藤 恵一, Markus Enders, 山下 正廣
    • Organizer
      第64回錯体化学討論会
    • Place of Presentation
      中央大学
    • Year and Date
      2014-09-18 – 2014-09-20
    • Related Report
      2014 Annual Research Report
  • [Presentation] Magnetic Properties of Terbium(III)–Fused Phthalocyaninato Triple-Decker Complex2014

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      41st International Conference on Coordination Chemistry
    • Place of Presentation
      Suntec Singapore International Convention & Exhibition Centre, Singapore
    • Year and Date
      2014-07-21 – 2014-07-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] Magnetic Properties of Terbium(III)–Fused Phthalocyaninato Triple-Decker Complex2014

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      The 14th International Conference on Molecule-Based Magnets
    • Place of Presentation
      Holiday Inn Moskovskye Vorota, Saint Petersburg, Russia
    • Year and Date
      2014-07-21 – 2014-07-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] テルビウム(III)-拡張フタロシアニン積層型錯体の磁気特性2014

    • Author(s)
      守田 峻海, 加藤 恵一, 高石 慎也, 山下 正廣
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学、名古屋
    • Year and Date
      2014-03-28
    • Related Report
      2013 Annual Research Report
  • [Presentation] Magnetic Relaxation Analysis of Hetero-Tetranuclear Lanthanoid(III)-Phthalocyaninato Quintuple-Decker Complex2013

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      6^<th> French Research Organizations-Tohoku University Joint Workshop on Frontier Materials
    • Place of Presentation
      Tohoku University, Sendai, Japan
    • Year and Date
      2013-12-03
    • Related Report
      2013 Annual Research Report
  • [Presentation] Magnetic Relaxation Analysis of Hetero-Tetranuclear Lanthanoid(III)-Phthalocyaninato Quintuple-Decker Complex2013

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      4th Asian Conference on Coordination Chemistry
    • Place of Presentation
      International Convention Center, Jeju, Korea
    • Year and Date
      2013-11-05
    • Related Report
      2013 Annual Research Report
  • [Presentation] ヘテロ4核ランタノイド-フタロシアニンQuintuple-Decker型錯体の磁化緩和挙動の解析2013

    • Author(s)
      守田 峻海, 加藤 恵一, 高石 慎也, 山下 正廣
    • Organizer
      第63回錯体化学討論会
    • Place of Presentation
      琉球大学、沖縄
    • Year and Date
      2013-11-03
    • Related Report
      2013 Annual Research Report
  • [Presentation] Magnetic Relaxation Analysis of Tetranuclear Lanthanoid(III)-phthalocyaninato Single-Molecule Magnets2013

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      4th European Conference on Molecular Magnetism
    • Place of Presentation
      Karlsruhe Institute of Technology, Germany
    • Year and Date
      2013-10-07
    • Related Report
      2013 Annual Research Report
  • [Presentation] Dual Magnetic Relaxation Processes Observed for a Tetranuclear Terbium(III) Single-Molecule Magnet with a Fused Phthalocyaninato Ligand having Two Coordination Sites2013

    • Author(s)
      Takaumi Morita, Keiichi Katoh, Brian K. Breedlove, Masahiro Yamashita
    • Organizer
      International Symposium for the 70th Anniversary of the Tohoku Branch of the Chemical Society of Japan
    • Place of Presentation
      Tohoku University, Sendai, Japan
    • Year and Date
      2013-09-28
    • Related Report
      2013 Annual Research Report

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Published: 2014-01-29   Modified: 2024-03-26  

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