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Synthesis and detailed analysis of magnetic anisotropy of lanthanide single-molecule magnets using ligands with cationic moieties

Research Project

Project/Area Number 20K05540
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionNara Women's University

Principal Investigator

KAJIWARA Takashi  奈良女子大学, 自然科学系, 教授 (80272003)

Project Period (FY) 2020-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2022: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2021: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2020: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Keywordsランタノイド錯体 / 磁気特性 / 遅い磁化緩和 / 希土類錯体 / 結晶構造 / 磁化率 / 希土類金属錯体 / 磁気異方性 / 分子構造 / 単分子磁石 / 配位子合成
Outline of Research at the Start

希土類化合物を対象に、分子構造の制御に基づいて特性の優れた単分子磁石の創生を目的とする。配位原子のルイス塩基性、酸性を適切に制御することによって結晶場の異方性の強化ができれば、従来よりも特性の優れた単分子磁石の構築が可能となる。ルイス酸性度の比較的高いピラジン環を基本骨格に持つ配位子系を対象に様々な希土類錯体を合成し、磁気特性の良否を分子構造との相関により解明する。

Outline of Final Research Achievements

We have synthesized lanthanide complexes with three-fold symmetry using ligands that contain coordination sites to cations such as alkali metal ions, and investigated the mechanism of the slow relaxation both from experimental and theoretical aspects. Gd(III) complexes exhibit slow magnetic relaxation up to 40 K even though they are isotropic lanthanide complexes, and we found the importance of the Raman process as a relaxation pathway. The importance of low-energy vibrations in crystals in the slow relaxation was revealed, and it was also found that the relaxation rate of magnetization varies greatly depending on the difference in the 2-D or 3-D network structure formed by the replacement of alkali metal ions, or on the hardness of the crystal.

Academic Significance and Societal Importance of the Research Achievements

分子レベルで遅い磁化緩和を示すランタノイド錯体は単分子磁石という名称で知られており、その磁気特性の向上は分子内における磁気異方性の良否という面で議論をされてきた。一方で、分子が集積することによって形成される結晶において、結晶を伝わる熱振動がタンう分子磁石の磁気特性に大きく影響することが知られており、特に結晶内に観測される低エネルギーの熱振動(格子振動)のなす役割について近年盛んに議論されている。本研究では結晶工学的な手法に基づいて遅い磁化緩和の特性向上を議論しており、今後の単分子磁石の分子デバイスへの応用に向けて、磁気特性の向上への指針を示すことに成功している。

Report

(5 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • 2021 Research-status Report
  • 2020 Research-status Report
  • Research Products

    (10 results)

All 2023 2022 2020 Other

All Int'l Joint Research (2 results) Journal Article (5 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 4 results,  Open Access: 1 results) Presentation (3 results) (of which Invited: 1 results)

  • [Int'l Joint Research] Institute of Nuclear Physics(ポーランド)

    • Related Report
      2023 Annual Research Report
  • [Int'l Joint Research] Institute of Nuclear Physics(ポーランド)

    • Related Report
      2020 Research-status Report
  • [Journal Article] Slow Magnetic Relaxation of Linear Trinuclear M(II)-Gd(III)-M(II) Complexes with D3 Point Group Symmetry (M(II) = Zn(II) and Mg(II))2023

    • Author(s)
      Masuda Yuka、Sakata Shiomi、Kayahara Saori、Irie Natsumi、Kofu Maiko、Kono Yohei、Sakakibara Toshiro、Horii Yoji、Kajiwara Takashi
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 127 Issue: 6 Pages: 3295-3306

    • DOI

      10.1021/acs.jpcc.2c08323

    • Related Report
      2023 Annual Research Report 2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Construction of a two-dimensional metal-organic framework with perpendicular magnetic anisotropy composed of single-molecule magnets2023

    • Author(s)
      Aratani Ikumi、Horii Yoji、Takajo Daisuke、Kotani Yoshinori、Osawa Hitoshi、Kajiwara Takashi
    • Journal Title

      Journal of Materials Chemistry C

      Volume: 11 Issue: 6 Pages: 2082-2088

    • DOI

      10.1039/d2tc04963e

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Rotating magnetocaloric effect in highly anisotropic Tb(III) and Dy(III) single molecular magnets2022

    • Author(s)
      Konieczny Piotr、Czernia Dominik、Kajiwara Takashi
    • Journal Title

      Scientific Reports

      Volume: 12 Issue: 1

    • DOI

      10.1038/s41598-022-20893-2

    • Related Report
      2022 Research-status Report
  • [Journal Article] Solid polymorphism and dynamic magnetic properties of a dodecylated vanadyl-porphyrinato complex: spin-lattice relaxations modulated by phase stabilisation2022

    • Author(s)
      Horii Yoji、Makino Momo、Yamamoto Taro、Tatsumi Shoichi、Suzuki Hal、Noguchi Mariko、Yoshida Takefumi、Kajiwara Takashi、Li Zhao-Yang、Yamashita Masahiro
    • Journal Title

      Inorganic Chemistry Frontiers

      Volume: 9 Issue: 23 Pages: 6271-6278

    • DOI

      10.1039/d2qi01607a

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Anisotropy of Spin?Lattice Relaxations in Mononuclear Tb3+ Single-Molecule Magnets2020

    • Author(s)
      Konieczny Piotr、Pelka Robert、Masuda Yuka、Sakata Shiomi、Kayahara Saori、Irie Natsumi、Kajiwara Takashi、Baran Stanislaw
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Issue: 14 Pages: 7930-7937

    • DOI

      10.1021/acs.jpcc.9b11057

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] 希土類を基盤とする単分子磁石の構築~異方性の設計と今後の課題2023

    • Author(s)
      梶原孝志
    • Organizer
      第39回希土類討論会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] Gd(III) 単核錯体における遅い磁化緩和と集積化が磁気特性に及ぼす効果2023

    • Author(s)
      村井文歌・池田郷愛・上岡萌音・上岡詩歩・堀井洋司・梶原孝志
    • Organizer
      日本化学会 第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] 18員環ポリアミンを基盤とする6座かご型配位子を用いた単核希土類金属錯体の合成、構造と遅い磁化緩和の発現2023

    • Author(s)
      堀井彩可・中村有稀・堀井洋司・梶原孝志
    • Organizer
      日本化学会 第103春季年会
    • Related Report
      2022 Research-status Report

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Published: 2020-04-28   Modified: 2025-01-30  

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