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Molecular systems with external field induced state conversions

Research Project

Project/Area Number 18K19088
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
Research InstitutionUniversity of Tsukuba

Principal Investigator

Oshio Hiroki  筑波大学, 数理物質系(名誉教授), 名誉教授 (60176865)

Co-Investigator(Kenkyū-buntansha) 大谷 亮  九州大学, 理学研究院, 准教授 (30733729)
Project Period (FY) 2018-06-29 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Fiscal Year 2020: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2019: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2018: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywords錯体化学 / 分子磁性 / 外場応答性分子 / 外場誘起電子状態変換 / スピンクロスオーバー / 混合原子価錯体 / 金属錯体 / 水素結合 / 磁性 / 電子移動 / 固体 / 双安定性 / 誘電性 / スピン平衡錯体
Outline of Final Research Achievements

This study aimed to construct spin crossover (SCO) and mixed valence (ET) complexes showing the external field-induced electronic state conversion.
(1) SCO complexes with di-basic/acid ligands were synthesized, and it was shown that the protonation of the ligands could convert the spin state. (2) Cyanide ion-bridged mixed-valence complexes were synthesized. The complexes exhibited that the intermolecular ππ interactions produce stresses on the coordination structure, resulting in significant differences in the external field-induced phase transition temperature. (3) In two-dimensional SCO complexes, we realized a system in which the SCO and the dielectric response are coupled by the coupling between the SCO and the rotation of the pyrazole group in the bridging ligand.

Academic Significance and Societal Importance of the Research Achievements

金属酸化物は強い電子相関に基づく強磁性・強誘電・電気伝導性を示し、これら物性を光・電場・磁場で制御するマルチフェロイックシステムが実現しつつある。一方、分子性化合物においては柔軟な構造・電子状態をもつにもかかわらず,その酸化状態・スピン状態の組合せに基づく光物性・磁性・電気的性質が強く結合する系は極めて少なく、高効率で高速な物性変換分子システムの構築が必要である。本研究では、スピンクロスオーバ錯体や混合原子価錯体集合体に、配位子のプロトン脱離・付加や分子間相互作用の導入により、将来の分子デバイスの基盤となる高度な物性変換システムシステムを構築することができた。

Report

(6 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • 2020 Research-status Report
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (34 results)

All 2022 2021 2020 2019 2018 Other

All Int'l Joint Research (5 results) Journal Article (18 results) (of which Int'l Joint Research: 13 results,  Peer Reviewed: 18 results,  Open Access: 1 results) Presentation (10 results) (of which Int'l Joint Research: 9 results,  Invited: 2 results) Book (1 results)

  • [Int'l Joint Research] Dalian University of Technology(中国)

    • Related Report
      2022 Annual Research Report
  • [Int'l Joint Research] Dalian University of Technology(中国)

    • Related Report
      2021 Research-status Report
  • [Int'l Joint Research] Nottingham University(英国)

    • Related Report
      2019 Research-status Report
  • [Int'l Joint Research] Dalian Univesity of Technology(中国)

    • Related Report
      2019 Research-status Report
  • [Int'l Joint Research] University of Valencia(スペイン)

    • Related Report
      2019 Research-status Report
  • [Journal Article] Spin‐Crossover Tuned Rotation of Pyrazolyl Rings in a 2D Iron(II) Complex towards Synergetic Magnetic and Dielectric Transitions2022

    • Author(s)
      Wen Wen、Liu Qiang、Zhang Shi‐Hui、Yao Nian‐Tao、Oshio Hiroki、Meng Yin‐Shan、Liu Tao
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 61 Issue: 34

    • DOI

      10.1002/anie.202208886

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Simultaneous Photo‐Induced Magnetic and Dielectric Switching in an Iron(II)‐Based Spin‐Crossover Hofmann‐Type Metal‐Organic Framework2022

    • Author(s)
      Yao Nian‐Tao、Zhao Liang、Sun Hui‐Ying、Yi Cheng、Guan Ya‐Hui、Li Ya‐Ming、Oshio Hiroki、Meng Yin‐Shan、Liu Tao
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 61 Issue: 45

    • DOI

      10.1002/anie.202208208

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photoinduced magnetic hysteresis in a cyanide-bridged two-dimensional [Mn2W] coordination polymer2022

    • Author(s)
      Zhu Hai-Lang、Meng Yin-Shan、Hu Ji-Xiang、Oshio Hiroki、Liu Tao
    • Journal Title

      Inorganic Chemistry Frontiers

      Volume: 9 Issue: 19 Pages: 4974-4981

    • DOI

      10.1039/d2qi01101h

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Manipulating Selective Metal-to-Metal Electron Transfer to Achieve Multi-Phase Transitions in an Asymmetric [Fe2Co]-Assembled Mixed-Valence Chain2022

    • Author(s)
      Nian-Tao Yao, Dr. Liang Zhao, Cheng Yi, Qiang Liu, Prof. Ya-Ming Li, Dr. Yin-Shan Meng, Hiroki Oshio, Tao Liu
    • Journal Title

      Angew. Chem. Int. Ed.hem.

      Volume: 61 Issue: 11

    • DOI

      10.1002/anie.202115367

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis of a Ru(II) Complex with a Naphthoquinone-Annelated Imidazole Ligand Exhibiting Proton-Responsive Redox and Luminescent Behavior2021

    • Author(s)
      Takuya Shiga, Minami Tachibana, Hiroki Oshio and Masayuki Nihei
    • Journal Title

      Inorganics

      Volume: 9 Pages: 24-33

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Heteroleptic iron(II) complexes with naphthoquinone-type ligands2020

    • Author(s)
      Takuya Shiga, Rina Kumamaru, Graham N. Newton, Hiroki Oshio
    • Journal Title

      Dalton Trans.

      Volume: 49 Pages: 1485-1491

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A Ferromagnetically Coupled Octanuclear Manganese(III) Cluster: A Single-Molecule Magnet with a Spin Ground State2020

    • Author(s)
      Takuya Shiga, Hiroyuki Nojiri, Hiroki Oshio
    • Journal Title

      Inorg. Chem.

      Volume: 59 Pages: 4163-4166

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Effect of Intermolecular Interactions on Metal-to-Metal Charge Transfer: A Combined Experimental and Theoretical Investigation2019

    • Author(s)
      Cheng-Qi Jiao, Yin-Shan Meng, Yang Yu, Wen-Jing Jiang, Wen Wen, Hiroki Oshio, Yi Luo, Chun-Ying Duan, Tao Liu
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 58 Pages: 17009-17015

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A triple-triangle cluster derived from a simple tridentate ligand2019

    • Author(s)
      Takuya Shiga, Natsumi Okawa, Hiroki Oshio
    • Journal Title

      Dalton Trans

      Volume: 48 Pages: 17437-17440

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] A Bronsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States2019

    • Author(s)
      Shiga Takuya、Saiki Ryo、Akiyama Lisa、Kumai Reiji、Natke Dominik、Renz Franz、Cameron Jamie M.、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 17 Pages: 5658-5662

    • DOI

      10.1002/anie.201900909

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Substituent dependence on the spin crossover behaviour of mononuclear Fe(ii) complexes with asymmetric tridentate ligands2019

    • Author(s)
      Saiki Ryo、Miyamoto Haruka、Sagayama Hajime、Kumai Reiji、Newton Graham N.、Shiga Takuya、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 48 Issue: 10 Pages: 3231-3236

    • DOI

      10.1039/c9dt00204a

    • NAID

      120007133433

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Structure Switching and Modulation of the Magnetic Properties in Diarylethene-Bridged Metallosupramolecular Compounds by Controlled Coordination-Driven Self-Assembly2019

    • Author(s)
      Li Zhao-Yang、Dai Jing-Wei、Damjanovic Marko、Shiga Takuya、Wang Jin-Hua、Zhao Jia、Oshio Hiroki、Yamashita Masahiro、Bu Xian-He
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 13 Pages: 4339-4344

    • DOI

      10.1002/anie.201900789

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Ferrihydrite Particle Encapsulated within a Molecular Organic Cage2018

    • Author(s)
      Nihei Masayuki、Ida Hiromichi、Nibe Takayuki、Moeljadi Adhitya Mangala Putra、Trinh Quang Thang、Hirao Hajime、Ishizaki Manabu、Kurihara Masato、Shiga Takuya、Oshio Hiroki
    • Journal Title

      Journal of the American Chemical Society

      Volume: 140 Issue: 50 Pages: 17753-17759

    • DOI

      10.1021/jacs.8b10957

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Carboxylic Acid Functionalized Spin-Crossover Iron(II) Grids for Tunable Switching and Hybrid Electrode Fabrication2018

    • Author(s)
      Shiga Takuya、Sato Yamato、Tachibana Minami、Sato Hiroki、Matsumoto Takuto、Sagayama Hajime、Kumai Reiji、Murakami Youichi、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Inorganic Chemistry

      Volume: 57 Issue: 22 Pages: 14013-14017

    • DOI

      10.1021/acs.inorgchem.8b01856

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Two-electron redox-active tricyano iron(ii) complex with 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine as a building block for coordination polymers2018

    • Author(s)
      Shiga Takuya、Miyamoto Haruka、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 38 Pages: 13402-13407

    • DOI

      10.1039/c8dt02315h

    • NAID

      120007133434

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Cobalt complexes with redox-active anthraquinone-type ligands2018

    • Author(s)
      Shiga Takuya、Kumamaru Rina、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 23 Pages: 7804-7811

    • DOI

      10.1039/c8dt00586a

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Post-functionalization of a photoactive hybrid polyoxotungstate2018

    • Author(s)
      Cameron Jamie M.、Fujimoto Satomi、Wei Rong-Jia、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 31 Pages: 10590-10594

    • DOI

      10.1039/c8dt01253a

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Pre-programmed self-assembly of polynuclear clusters2018

    • Author(s)
      Shiga Takuya、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 22 Pages: 7384-7394

    • DOI

      10.1039/c8dt00822a

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Charge transfer interactions in molecular magnetism2019

    • Author(s)
      Hiroki Oshio
    • Organizer
      12th European School on Molecular Nanoscience and 7th Workshop on 2D Materials
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Metal complexes with multi accessible electronic states2019

    • Author(s)
      Hiroki Oshio
    • Organizer
      The fourth Chinese Conference of Molecular Magnetism Symposium on the Frontiers of Molecular Magnetism in China
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] グリッド型スピン平衡錯体の集積化を目指した新規鉄錯体の合成と物性2018

    • Author(s)
      立花 美奈水、志賀 拓也、大塩 寛紀
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Multi-nuclear Cluster as a Functional Unit of Bulk Materials2018

    • Author(s)
      M. Nihei, Y. Yanai, M. Kato, H. Oshio
    • Organizer
      International Conference on Coordination Chemistry, 2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Spin Crossover Iron(II) Grid Complexes2018

    • Author(s)
      Takuya SHIGA, Hiroki OSHIO
    • Organizer
      International Conference on Coordination Chemistry, 2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Multi-Response Bistability in Chiral Metal Complexes2018

    • Author(s)
      Rong-Jia Wei, Takuya Shiga, Hiroki Oshio*
    • Organizer
      International Conference on Coordination Chemistry, 2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Electronic state conversions of iron complexes with Brensted acid and base2018

    • Author(s)
      Ryo SAIKI, Lisa AKIYAMA, Takuya SHIGA, Franz RENZ, Hiroki OSHIO
    • Organizer
      International Conference on Coordination Chemistry, 2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] redox-active tricyano iron(II) complex with 2,4,6-tris(2- pyrimidyl)-1,3,5-triazine as a building block for coordination polymers2018

    • Author(s)
      Haruka MIYAMOTO, Takuya SHIGA, Graham N. NEWTON, Hiroki OSHIO
    • Organizer
      International Conference on Coordination Chemistry, 2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Control of Electron Transition in a Cyanide-Bridged [Co2Fe2] Square Complex by a Bifunctional Hydrogen Donor2018

    • Author(s)
      D. Natke, M. Nihei, H. Oshio, F. Renz
    • Organizer
      International Conference on Coordination Chemistry, 2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Hydrogen Bond Networks Constructed by a Cyanide-Bridged Tetranuclear Complex2018

    • Author(s)
      R. Takayama, M. Kato, M. Nihei, H. Oshio
    • Organizer
      International Conference on Coordination Chemistry, 2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Book] 分子磁性2022

    • Author(s)
      大塩寛紀
    • Total Pages
      170
    • Publisher
      共立出版
    • ISBN
      9784320044791
    • Related Report
      2020 Research-status Report

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Published: 2018-07-25   Modified: 2024-01-30  

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