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A Spin-Crossover High-Spin Phase Can Be a Magnetically Ordered Phase?

Research Project

Project/Area Number 22K19006
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 32:Physical chemistry, functional solid state chemistry, and related fields
Research InstitutionThe University of Electro-Communications

Principal Investigator

Ishida Takayuki  電気通信大学, 大学院情報理工学研究科, 教授 (00232306)

Co-Investigator(Kenkyū-buntansha) 畑中 信一  宇都宮大学, 大学教育推進機構, 特任准教授 (40334578)
小林 義男  電気通信大学, 大学院情報理工学研究科, 教授 (30221245)
Project Period (FY) 2022-06-30 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2023: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Fiscal Year 2022: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywordsスピン転移 / スピンクロスオーバー / 構造相転移 / MOF / ラジカル / 鉄(II)錯体 / 有機ラジカル / d-π相互作用 / 機械学習 / 磁性材料 / 磁気転移
Outline of Research at the Start

分子磁性研究者にとって室温で動作する磁石の開発は悲願である。純有機/分子磁石は磁気転移温度が極低温であることが難点であったから、実用温度とするには、パラダイムシフトが必要であった。本課題では構造転移を用いて解決を図る。磁気転移はいわゆる二次転移であって、分子や結晶の幾何は維持される。一方、スピンクロスオーバー(SCO)は一次転移である(結合長等が変化)。この構造変換が磁気転移を誘起するシナリオにより、高温(例えば室温)で動作する分子性磁性材料を得ることが目的である。本申請は、低温側で無秩序相、高温側で秩序相になるという常識に反する命題の実践であり、高い挑戦性がある。

Outline of Final Research Achievements

The results are listed as follows. (1) Controllable hysteresis in iron(II) spin-crossover materials. (2) Solid-state organic spin transition as a dynamic covalent chemistry. (3) Intramolecular solid-state organic spin transition. (4) Singlet/triplet ground spin-state switch in bisnitroxide materials. (5) Two-dimensional coordination polymers of rare-earth coordination materials. (6) Development of spin-crossover ligands carrying a radical group. In conclusion, we developed several room-temperature spin-crossover complexes and room-temperature organic spin-transition compounds. Furthermore, we studied the possibility of control of magnetic interactions and cooperativities and extension to high-dimensional magnetic networks. Several checkpoints of the present project have been cleared.

Academic Significance and Societal Importance of the Research Achievements

分子磁性研究者にとって室温で動作する磁石の開発は悲願である。純有機/分子磁石は磁気転移温度が極低温であることが難点(例えば液体He温度以下)であったから、実用温度とするには、パラダイムシフトが必要であった。本課題では構造転移を用いて解決を図る。この構造変換が磁気転移を誘起するシナリオにより、室温で動作する分子性磁性材料を得ることが目的である。分子磁性という学問分野は我国が世界に誇れる基幹物理化学の一つであって、この分野発の新規材料群で、学界・産業界に貢献することは意義深い。これまでに有機強磁性体や超高スピン分子は開発済みであるが、分子磁性分野からの応用展開は、国内外でまだ実績がない。

Report

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

    (24 results)

All 2024 2023 2022 Other

All Int'l Joint Research (3 results) Journal Article (6 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 6 results,  Open Access: 2 results) Presentation (13 results) (of which Int'l Joint Research: 7 results) Remarks (2 results)

  • [Int'l Joint Research] Cukurova University(トルコ)

    • Related Report
      2023 Annual Research Report
  • [Int'l Joint Research] Massey University(ニュージーランド)

    • Related Report
      2023 Annual Research Report
  • [Int'l Joint Research] Cukurova University(トルコ)

    • Related Report
      2022 Research-status Report
  • [Journal Article] Biradical pincers involving two phenylene, biphenylene or terphenylene arms: Evidence for approach of two terminal nitroxides2024

    • Author(s)
      Rika Uesugi, Rina Takano, Takayuki Ishida
    • Journal Title

      Tetrahedron

      Volume: 156 Pages: 133929-133929

    • DOI

      10.1016/j.tet.2024.133929

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Temperature-scan-rate dependent SCO hysteresis found in a tetramethylphosphonium tripodal ferrate(II) salt2024

    • Author(s)
      Masaru Yamasaki , Yoshimasa Noguchi , Takayuki Ishida
    • Journal Title

      Inorganica Chimica Acta

      Volume: 569

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Metal-Organodiphosphonate Chemistry: Hydrothermal Syntheses and Structures of Two Novel Copper(II) Coordination Polymers with o-Xylylenediphosphonic Acid and 4,4′-Bipyridine Ligands2023

    • Author(s)
      Burak Ay, Rina Takano, Takayuki Ishida
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 96 Issue: 10 Pages: 1129-1138

    • DOI

      10.1246/bcsj.20230160

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Continuous Condensed Triplet Accumulation for Irradiance‐Induced Anticounterfeit Afterglow2023

    • Author(s)
      Ende Hopsah Badriyah, Kikuya Hayashi, Bahadur Sk, Rina Takano, Takayuki Ishida, Shuzo Hirata*
    • Journal Title

      Advanced Science

      Volume: 10 Issue: 36 Pages: 2304374-2304374

    • DOI

      10.1002/advs.202304374

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] A Triplet/Singlet Ground-State Switch via the Steric Inhibition of Conjugation in 4,6-Bis(trifluoromethyl)-1,3-phenylene Bisnitroxide2023

    • Author(s)
      Nagito Haga , Takayuki Ishida
    • Journal Title

      Molecules

      Volume: 29

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis, crystal structure, and luminescence properties of a three-dimensional coordination polymer from europium(III) carbonate hemioxalate hydrate2022

    • Author(s)
      Rina Takano, Takayuki Ishida and Burak Ay
    • Journal Title

      CrystEngComm

      Volume: 24 Issue: 44 Pages: 7786-7792

    • DOI

      10.1039/d2ce01105k

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Stereoisomeric Effect on Spin Crossover in Iron(II) Bisdiimine Dithiocyanates2023

    • Author(s)
      R. Takano, M. Yoshida, B. Ay, N. Mochida, Y. Kobayashi, and T. Ishida
    • Organizer
      The 18th International Conference on Molecule-Based Magnets (ICMM2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Mono- and Trinuclear Lanthanide Complexes Derived from Highly Symmetrical Ligand 2,4,6-Tris(2-pyrimidyl)-1,3,5-triazine: Synthesis, Structure and Magnetic Properties2023

    • Author(s)
      B. Ay and T. Ishida
    • Organizer
      The 18th International Conference on Molecule-Based Magnets (ICMM2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Systematic Study on Magnetic Properties of Bilayered Heavy Lanthanide Squarate Hydrates2023

    • Author(s)
      R. Takano, K. Masuda, Y. Kitagawa, M. Kofu, S. Ohira-Kawamura, and T. Ishida
    • Organizer
      The 18th International Conference on Molecule-Based Magnets (ICMM2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Naphthalene-1,8-diyl Bis(tert-butyl Nitroxide) for a Para-/Diamagnetic Switching Material2023

    • Author(s)
      R. Uesugi and T. Ishida
    • Organizer
      The 18th International Conference on Molecule-Based Magnets (ICMM2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Dia-/Paramagnetic Distinguishable Phases in Bisnitroxide Crystals2023

    • Author(s)
      S. Ueno, R. Uesugi, and T. Ishida
    • Organizer
      The 9th International Conference on Nitroxide Radicals (SPIN-2023)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] pH effect on hydrothermal synthesis of the copper organodiphosphonate polymers: Investigation of luminescence and magnetic properties2023

    • Author(s)
      B. Ay and T. Ishida
    • Organizer
      The 103rd CSJ Annual Meeting
    • Related Report
      2022 Research-status Report
  • [Presentation] Photoluminescence Properties of a Three-Dimensional Coordination Polymer from Rare Earth Ion and Small Ligands2023

    • Author(s)
      R. Takano, B. Ay, and T. Ishida
    • Organizer
      The 103rd CSJ Annual Meeting
    • Related Report
      2022 Research-status Report
  • [Presentation] o-キシリレンジオキシを蝶番に用いたピンセット型テトラニトロキシドラジカルの分子内ラジカル間相互作用2023

    • Author(s)
      上杉莉加・石田尚行
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] Key to Tune Crystal Field for Spin Crossover in Dinuclear Iron(II) Helicates with Diimine Ligands2022

    • Author(s)
      R. Takano, Y. Kobayashi, and T. Ishida
    • Organizer
      The 44th International Conference on Coordination Chemistry (ICCC 2022)
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research
  • [Presentation] Chains and Macrocycles of Heavy Lanthanide Ions Bridged with a Triplet Biradical2022

    • Author(s)
      T. Ishida, S. Ito, S. Ueno, and S.-i. Hatanaka
    • Organizer
      The 44th International Conference on Coordination Chemistry (ICCC 2022)
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research
  • [Presentation] Magnetic Properties of Polymeric Bilayer Complexes of Heavy Lanthanide Ions Bridged with a Dianionic Squarate2022

    • Author(s)
      R. Takano, T. Ishida
    • Organizer
      第72回錯体化学討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] 常磁性/反磁性スイッチング材料を目指したo-キシリレンジオキシにより架橋されたビスニトロキシドラジカル2022

    • Author(s)
      上杉莉加・山口慶来・石田尚行
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] 立体的に嵩高い置換基を持つ1,3-フェニレンビスニトロキシドラジカルの反磁性・常磁性転移2022

    • Author(s)
      上野隼弥・石田尚行
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Research-status Report
  • [Remarks] 石田研究室ホームページ

    • URL

      http://ttf.pc.uec.ac.jp

    • Related Report
      2023 Annual Research Report
  • [Remarks] 石田研究室ホームページ

    • URL

      http://ttf.pc.uec.ac.jp/www.page/Ishida.html

    • Related Report
      2022 Research-status Report

URL: 

Published: 2022-07-05   Modified: 2025-01-30  

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