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Development of Electric Field- and Photo-responsive Multinuclear Complex Based on Proton Transfer Coupled Spin Transition

Research Project

Project/Area Number 22K14658
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 32020:Functional solid state chemistry-related
Research InstitutionTohoku University (2023)
Kyushu University (2022)

Principal Investigator

Nakanishi Takumi  東北大学, 金属材料研究所, 助教 (40836425)

Project Period (FY) 2022-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2023: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Fiscal Year 2022: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywords水素結合 / プロトン移動 / スピン転移 / 中性子回折測定 / 光応答 / ヒドラゾン錯体 / 遷移金属錯体 / 電場応答 / 多核錯体
Outline of Research at the Start

本研究では、電場による物性制御が可能な分子性物質の開拓を目的に、プロトン移動とスピン転移が連動して発現する現象(プロトン結合スピン転移現象)を発現する遷移金属錯体の開発を行う。特に、近年開発した分子内水素結合を有するキラル二座配位子と金属イオン間を架橋する配位子を用いることで、磁気的相互作用をもたらす三次元ネットワークを形成した多核錯体を構築する。熱および電場誘起プロトン移動と連動したスピン転移により強磁性-反強磁性のON-OFFが可能な分子性材料の開発を目指す。

Outline of Final Research Achievements

In this study, We developed a new ligand and PCST complex based on salicylhydrazide that can be extended to multinuclear complexes and introduce functional moieties, for the exploration of new functions based on the proton transfer coupled spin transition (PCST) phenomenon. The new ligands and iron(II) complexes were synthesized by the investigation of the optimal combination of substituents suitable for the occurrence of PCST. The X-ray and neutron structure measurement of obtained iron(II) complex revealed that the proton in both two ligands show the proton transfer coupled with photo- and thermal spin transition. Based on these results, we have succeeded in developing a new ligand that can extend the design of PCST complex.

Academic Significance and Societal Importance of the Research Achievements

これまでのプロトン結合スピン転移現象の研究では基礎的な観点から、スピン転移現象との連動に基づく新規プロトン移動現象の開拓を進めてきた。一方で、プロトン移動に基づく機能開拓を進める上で、従来のプロトン結合スピン転移錯体の設計では特徴的な構造要素(電子受容/供与性やキラリティーなど)を有する置換基や配位子の導入による物質探索が困難であるという課題があった。本研究で新たに開発した配位子は多様な置換基を導入可能な部位を有しており、また二座や四座配位子への拡張が可能であることから、架橋配位子に基づく多核錯体化やキラル部位の導入による極性構造の形成など従来では困難であった物質設計が実現出来ると期待される。

Report

(3 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • Research Products

    (3 results)

All 2023

All Journal Article (2 results) (of which Peer Reviewed: 2 results) Presentation (1 results)

  • [Journal Article] Development of an Iron(II) Complex Exhibiting Thermal- and Photoinduced Double Proton-Transfer-Coupled Spin Transition in a Short Hydrogen Bond2023

    • Author(s)
      Nakanishi Takumi、Hori Yuta、Shigeta Yasuteru、Sato Hiroyasu、Kiyanagi Ryoji、Munakata Koji、Ohhara Takashi、Okazawa Atsushi、Shimada Rintaro、Sakamoto Akira、Sato Osamu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 145 Issue: 35 Pages: 19177-19181

    • DOI

      10.1021/jacs.3c06323

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Observation of Proton-Transfer-Coupled Spin Transition by Single-Crystal Neutron-Diffraction Measurement2023

    • Author(s)
      Takumi Nakanishi, Yuta Hori, Yasuteru Shigeta, Hiroyasu Sato, Shu-Qi Wu, Ryoji Kiyanagi, Koji Munakata, Takashi Ohhara and Osamu Sato
    • Journal Title

      Phys. Chem. Chem. Phys.

      Volume: - Issue: 17 Pages: 12394-12400

    • DOI

      10.1039/d3cp00527e

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Presentation] 結晶中における光および熱を利用した多様なプロトン移動現象の制御2023

    • Author(s)
      中西 匠、佐藤 治
    • Organizer
      錯体化学会第73回討論会
    • Related Report
      2023 Annual Research Report

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Published: 2022-04-19   Modified: 2025-01-30  

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