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Fabrication of charge-transfer assembled thin films by electrochemical methods and control of magnetic property

Research Project

Project/Area Number 19K15518
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 32020:Functional solid state chemistry-related
Research InstitutionKumamoto University (2020)
Tohoku University (2019)

Principal Investigator

Sekine Yoshihiro  熊本大学, 大学院先導機構, 准教授 (40733465)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2020: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2019: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords金属錯体化学 / 電子ドナー・アクセプター / 磁性 / 薄膜
Outline of Research at the Start

金属錯体や有機ラジカルを基盤とした分子磁性が始まり約40年経つが、舞台はバルク(結晶や粉末)が中心で、薄膜はあまり例がない。これは対象の分子磁性体に適した薄膜構築法が未開拓であり、系統的な合成が困難だったためである。バルクと比べて薄膜は①サイズ制御可能で②透明性を有し③外場による物性変調が容易という複数の利点を持つので、機能発現へと展開できる。対象物質は電子ドナー(D)とアクセプター(A)が共有結合的に連結した多孔性磁石(D/A-MOF)であり、電荷/スピン/格子を協奏的に制御可能な化合物群である。D/A-MOFの薄膜構築法を確立し、電気化学的手法による高速な磁気機能制御を達成する。

Outline of Final Research Achievements

In this study, we have investigated the charge-transfer assemblies (D/A-MOFs), in which the electron donor (D) and acceptor (A) are covalently linked, for constructing thin films materials and switching their electronic and magnetic properties. We have successfully constructed charge-transfer aggregate thin films by electrochemical deposition method using a carboxylate-bridged diruthenium complex (D) and a TCNQ derivative (A). Furthermore, we have fabricated a series of various D/A-MOF thin films. We also achieved reversible and fast switching of electronic states in D/A-MOF thin films by electrochemical redox reaction.

Academic Significance and Societal Importance of the Research Achievements

外場応答性分子としてエレクトロクロミック分子やスピン転移化合物、pH応答発光分子など数多く報告されているが、電気化学的刺激によって磁気機能変換を示す分子性化合物は稀有である。本研究の対象物質が酸化還元活性な磁気格子であるため、電気化学的な電子輸送・イオン輸送に伴って高速な磁気機能変換が期待できる点は意義深い。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (12 results)

All 2021 2020 2019

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Open Access: 1 results) Presentation (7 results)

  • [Journal Article] Ionicity Diagrams for Electron-Donor and -Acceptor Metal?Organic Frameworks: DA Chains and D2A Layers Obtained from Paddlewheel-Type Diruthenium(II,II) Complexes and Polycyano-Organic Acceptors2021

    • Author(s)
      Sekine Yoshihiro、Nishio Masaki、Shimada Tomoka、Kosaka Wataru、Miyasaka Hitoshi
    • Journal Title

      Inorganic Chemistry

      Volume: 60 Issue: 5 Pages: 3046-3056

    • DOI

      10.1021/acs.inorgchem.0c03335

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Fine tuning of intra-lattice electron transfers through site doping in tetraoxolene-bridged iron honeycomb layers2020

    • Author(s)
      Sekine Yoshihiro、Chen Jian、Eguchi Naoki、Miyasaka Hitoshi
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 74 Pages: 10867-10870

    • DOI

      10.1039/d0cc03808c

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Electrochemical Development of Magnetic Long-Range Correlations with Tc = 128 K in a Tetraoxolene-Bridged Fe-Based Framework2020

    • Author(s)
      Jian Chen, Kouji Taniguchi, Yoshihiro Sekine, and Hitoshi Miyasaka
    • Journal Title

      J. Mag. Mag. Mater.

      Volume: 494 Pages: 165818-165818

    • DOI

      10.1016/j.jmmm.2019.165818

    • Related Report
      2020 Annual Research Report 2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chameleonic layered metal-organic frameworks with variable charge-ordered states triggered by temperature and guest molecules2020

    • Author(s)
      Chen Jian、Sekine Yoshihiro、Okazawa Atsushi、Sato Hiroyasu、Kosaka Wataru、Miyasaka Hitoshi
    • Journal Title

      Chemical Science

      Volume: - Issue: 14 Pages: 3610-3618

    • DOI

      10.1039/d0sc00684j

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Strong electronic influence of equatorial ligands on frontier orbitals in paddlewheel dichromium(ii,ii) complexes2019

    • Author(s)
      Huang Po-Jung、Natori Yoshiki、Kitagawa Yasutaka、Sekine Yoshihiro、Kosaka Wataru、Miyasaka Hitoshi
    • Journal Title

      Dalton Transactions

      Volume: 48 Issue: 3 Pages: 908-914

    • DOI

      10.1039/c8dt04347g

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] The development of stimuli-responsive metal complex2021

    • Author(s)
      Yoshihiro Sekine, Shinya Hayami
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Control of intra-lattice electron transfers in tetraoxolene-bridged two-dimensional honeycomb layers2021

    • Author(s)
      Yoshihiro Sekine, Hitoshi Miyasaka
    • Organizer
      1st Asian conference on Molecular Magnetism
    • Related Report
      2020 Annual Research Report
  • [Presentation] 電気的中性型テトラオキソレン架橋鉄ハニカム層状集積体の合理的設計と電子状態制御2021

    • Author(s)
      江口 尚輝、高坂 亘、関根 良博、宮坂 等
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Multi-responsive charge state switching in tetraoxolene-bridged Fe two-dimensional honeycomb layered frameworks2020

    • Author(s)
      Sekine Yoshihiro, Jian Chen, Kosaka Wataru, Miyasaka Hitoshi
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] テトラオキソレン架橋鉄二次元層状化合物における分子内電子移動制御2019

    • Author(s)
      関根 良博, 陳 健,岡澤 厚,宮坂 等
    • Organizer
      第13回分子科学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] Control of intra-lattice electron transfers in tetraoxolene-bridged two-dimensional layers2019

    • Author(s)
      Sekine Yoshihiro, Jian Chen, Okazawa Atsushi, Miyasaka Hitoshi
    • Organizer
      The 69th Conference of Japan Society of Coordination Chemistry
    • Related Report
      2019 Research-status Report
  • [Presentation] Control of Magnetism for Electrochemical Responsive thin film constructed by charge-transferred assembly of paddlewheel-type diruthenium complex and TCNQ derivatives2019

    • Author(s)
      SEKINE, Yoshihiro, MIYASAKA, Hitoshi
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2022-01-27  

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