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Structural elucidation and functional development of melts obtained by heating coordination polymer crystals

Research Project

Project/Area Number 21H01950
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionKyoto University

Principal Investigator

Horike Satoshi  京都大学, 理学研究科, 教授 (70552652)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000)
Fiscal Year 2023: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2022: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2021: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000)
Keywords配位高分子 / 金属ー有機構造体 / 融液 / ガラス / 結晶融解 / 金属-有機構造体 / 状態図 / 相転移 / 分子構造 / エントロピー / 機能性液体
Outline of Research at the Start

金属イオンと架橋性配位子から組み上がる配位高分子(Coordination Polymer, CP)は磁性、伝導性、光物性など多彩な特性が知られてきた。膨大な数のCP研究のほとんどは結晶相を対象としてきた。近年、一部のCP結晶を加熱して得られる「液体相」およびそれらを冷却して得られる「ガラス相」が見いだされた。一方、CPの融液の構造や機能は未だ研究がなされていない。本研究では多彩な結晶構造や特性を持つCPが融液となったとき、どのような構造や物性を示すのか、それらを先端解析と系統的合成によって取り扱う。この研究を通してCP融液を新たな機能性液体として提案する。

Outline of Final Research Achievements

The melting phenomenon of coordination polymer crystals was clarified in relation to the combination of metal and ligand and the dimensionality of the crystal structure. By using synchrotron radiation X-rays, solid-state NMR, and viscoelasticity measurements, it was possible to infer the structure in the melt state, and the understanding of the melting mechanism of coordination polymers was deepened. Furthermore, by cooling the melt under appropriate conditions, various glassy states can be created, which may lead to the development of new materials with functional properties such as ion conductivity and porosity. These findings are expected to broaden the range of applications of coordination polymers and serve as a guideline for designing functional materials, especially those using melts.

Academic Significance and Societal Importance of the Research Achievements

配位高分子のガラス相に関する研究が近年盛んに行われているものの、融液状態についての解析は皆無に等しく、その構造がガラス状態と類似しているのか、あるいは金属と配位子が解離しているのかなどの知見が欠如していた。このことは、配位高分子を機能性材料として設計する上で大きな障壁となっていた。本研究では、配位高分子の融液の多くがネットワーク性を有していることを明らかにし、分子構造のみならず、ファイバーや膜などのマクロ成形加工に関する重要な知見を提供した。これらの結果は、配位高分子ガラスや融液を利用した分離や伝導などの機能性材料へと発展させていく上で、非常に重要な指針となるものである。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Annual Research Report
  • 2021 Annual Research Report
  • Research Products

    (13 results)

All 2023 2022

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

  • [Journal Article] Glass and Liquid States of Coordination Polymer Crystals2023

    • Author(s)
      Horike Satoshi
    • Journal Title

      Bulletin of Japan Society of Coordination Chemistry

      Volume: 81 Issue: 0 Pages: 74-84

    • DOI

      10.4019/bjscc.81.74

    • ISSN
      1882-6954, 1883-1737
    • Year and Date
      2023-05-31
    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Photoexcited Anhydrous Proton Conductivity in Coordination Polymer Glass2023

    • Author(s)
      Ma Nattapol、Impeng Sarawoot、Bureekaew Sareeya、Morozumi Naoki、Haga Masa-aki、Horike Satoshi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 145 Issue: 17 Pages: 9808-9814

    • DOI

      10.1021/jacs.3c01821

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Heterogenous CO2 Reduction Photocatalysis of Transparent Coordination Polymer Glass Membranes Containing Metalloporphyrins2023

    • Author(s)
      Izu Hitoshi、Tabe Hiroyasu、Namiki Yuji、Yamada Hiroki、Horike Satoshi
    • Journal Title

      Inorganic Chemistry

      Volume: 62 Issue: 29 Pages: 11342-11349

    • DOI

      10.1021/acs.inorgchem.3c00700

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Formation of Porosity toward Acetylene upon Vitrification of Non-porous Photochromic Coordination Polymer Crystals2023

    • Author(s)
      Fan Zeyu、Wei Yong-Sheng、Tabe Hiroyasu、Nakatani Tomotaka、Das Chinmoy、Yamada Hiroki、Horike Satoshi
    • Journal Title

      Chemistry of Materials

      Volume: 35 Issue: 10 Pages: 3859-3866

    • DOI

      10.1021/acs.chemmater.2c03510

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Exploration of glassy state in Prussian blue analogues2022

    • Author(s)
      Ma Nattapol、Ohtani Ryo、Le Hung M.、Sorensen S. S.、Ishikawa Ryuta、Kawata Satoshi、Bureekaew Sareeya、Kosasang Soracha、Kawazoe Yoshiyuki、Ohara Koji、Smedskjaer Morten M.、Horike Satoshi
    • Journal Title

      Nature Communications

      Volume: 13 Issue: 1 Pages: 4023-4023

    • DOI

      10.1038/s41467-022-31658-w

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Photoluminescent coordination polymer bulk glasses and laser-induced crystallization2022

    • Author(s)
      Fan Zeyu、Das Chinmoy、Demessence Aude、Zheng Ruilin、Tanabe Setsuhisa、Wei Yong-Sheng、Horike Satoshi
    • Journal Title

      Chemical Science

      Volume: 13 Issue: 11 Pages: 3281-3287

    • DOI

      10.1039/d1sc06751f

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Metal-Organic Network-Forming Glasses2022

    • Author(s)
      Ma Nattapol、Horike Satoshi
    • Journal Title

      Chemical Reviews

      Volume: 122 Issue: 3 Pages: 4163-4203

    • DOI

      10.1021/acs.chemrev.1c00826

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Three-Dimensional Metal-Organic Network Glasses from Bridging MF6(2-) Anions and Their Dynamic Insights by Solid-State NMR2022

    • Author(s)
      Kurihara Takuya、Ohara Kotaro、Kadota Kentaro、Izu Hitoshi、Nishiyama Yusuke、Mizuno Motohiro、Horike Satoshi
    • Journal Title

      Inorganic Chemistry

      Volume: 61 Issue: 40 Pages: 16103-16109

    • DOI

      10.1021/acs.inorgchem.2c02580

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Network Size Control in Coordination Polymer Glasses and Its Impact on Viscosity and H<sup>+</sup> Conductivity2022

    • Author(s)
      Ogawa Tomohiro、Takahashi Kazuki、Kurihara Takuya、Nagarkar Sanjog S.、Ohara Koji、Nishiyama Yusuke、Horike Satoshi
    • Journal Title

      Chemistry of Materials

      Volume: 34 Issue: 13 Pages: 5832-5841

    • DOI

      10.1021/acs.chemmater.2c00494

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Modulation of proton conductivity in coordination polymer mixed glasses2022

    • Author(s)
      Thanaphatkosol Chonwarin、Ma Nattapol、Kageyama Kotoha、Watcharatpong Teerat、Tiyawarakul Thanakorn、Kongpatpanich Kanokwan、Horike Satoshi
    • Journal Title

      Chemical Communications

      Volume: 13 Issue: 41 Pages: 6064-6067

    • DOI

      10.1039/d2cc01266a

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Coordination polymer-forming liquid Cu(2-isopropylimidazolate)2022

    • Author(s)
      Watcharatpong Teerat、Pila Taweesak、Maihom Thana、Ogawa Tomohiro、Kurihara Takuya、Ohara Koji、Inoue Tadashi、Tabe Hiroyasu、Wei Yong-Sheng、Kongpatpanich Kanokwan、Horike Satoshi
    • Journal Title

      Chemical Science

      Volume: 13 Issue: 38 Pages: 11422-11426

    • DOI

      10.1039/d2sc03223f

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Eutectic CsHSO<sub>4</sub>-Coordination Polymer Glasses with Superprotonic Conductivity2022

    • Author(s)
      Ma Nattapol、Horike Nao、Lombardo Loris、Kosasang Soracha、Kageyama Kotoha、Thanaphatkosol Chonwarin、Kongpatpanich Kanokwan、Otake Ken-ichi、Horike Satoshi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 144 Issue: 40 Pages: 18619-18628

    • DOI

      10.1021/jacs.2c08624

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Crystallization Kinetics of a Liquid-Forming 2D Coordination Polymer2022

    • Author(s)
      Das Chinmoy、Nishiguchi Taichi、Fan Zeyu、Horike Satoshi
    • Journal Title

      Nano Letters

      Volume: 22 Issue: 23 Pages: 9372-9379

    • DOI

      10.1021/acs.nanolett.2c03207

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed

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Published: 2021-04-28   Modified: 2025-01-30  

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