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Control of Charge Arrangement and Electronic Phase Transition in Molecular Crystals

Research Project

Project/Area Number 20K05448
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 32020:Functional solid state chemistry-related
Research InstitutionKyoto University

Principal Investigator

Yamochi Hideki  京都大学, 理学研究科, 名誉教授 (20182660)

Co-Investigator(Kenkyū-buntansha) 大塚 晃弘  京都大学, 理学研究科, 准教授 (90233171)
Project Period (FY) 2020-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2022: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2021: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2020: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywords電荷配列 / 分子性結晶 / 電子相転移 / 導電性 / 磁性 / 電荷配置 / 電荷秩序 / 結晶構造
Outline of Research at the Start

本研究の主課題は、同符号かつ異なる荷電状態にある異種分子が周期的に配列した結晶構造(化学電荷秩序)を構築することにある。このために、形状やサイズが異なる分子を組合せることにより、結晶中の同一サイトに異種分子がランダムに充填した混晶の生成を防止することを試みる。さらに第1の成分分子として電荷を持つ置換基を有する分子を用い、同符号電荷間での静電反発による第1の成分分子どうしの接近を回避し、第1, 第2の成分分子が交互に充填された結晶の構築を試みる。
並行して強力な還元剤を用いた(ラジカル)陰イオン塩の作製も行い、分子結晶内での電荷分布様式の制御と電子物性の多様化を目指した実験研究を行う。

Outline of Final Research Achievements

The aim of this project was to construct the designing principles and the real substances for the functional molecular solids. This project succeeded in synthesizing the molecular conductor which simultaneously exhibits a metallic conductivity and single molecule magnet behavior by employing the well-recognized nature of known compounds. This study also examined the rarely applied concept of using (radical)anions of weak electron acceptor molecules which provided new metalloporphyrins, metallophthalocyanines and related metal-coordinated molecular (radical)anion species. The magnetic interactions within and between the coordination complex anions were thoroughly studied, including the revelation of the temperature-dependent spin quantum number, S.
This study has provided the unique molecular solids and the suggestive ideas to advance the fundamental sciences of materials.

Academic Significance and Societal Importance of the Research Achievements

本研究では成分分子に関する既知の特性を活かした新規導電性・磁性共存物質の開拓を行ったのみならず、電子受容性の弱い分子について前例の少ない(ラジカル)陰イオンとした状態での機能性物質の開拓が行われた。これらの研究指針は従来の物質開拓指針には欠けていた発想をも含み、その結果は機能性を持つ分子性結晶の開拓研究において新たな方法論を提示している。これらの成果から得られた知見は短期的に実用材料を産出するものではないが、固体物性科学分野における新たな基礎科学的な情報と物質設計指針の例を与えている。

Report

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

    (24 results)

All 2023 2022 2021 2020 Other

All Int'l Joint Research (5 results) Journal Article (16 results) (of which Int'l Joint Research: 16 results,  Peer Reviewed: 16 results,  Open Access: 3 results) Presentation (3 results)

  • [Int'l Joint Research] Institute of Solid State Physics, RAS/FRC Problem of Chem. Phys. MC, RAS(ロシア連邦)

    • Related Report
      2022 Annual Research Report
  • [Int'l Joint Research] Institute of Solid State Physics RAS(ロシア連邦)

    • Related Report
      2021 Research-status Report
  • [Int'l Joint Research] Ins. Problems of Chemical Physics RAS(ロシア連邦)

    • Related Report
      2021 Research-status Report
  • [Int'l Joint Research] Moscow State University(ロシア連邦)

    • Related Report
      2021 Research-status Report
  • [Int'l Joint Research] Institute of Solid State Physics RAS/Ins. Problems of Chemical Physics RAS/Moscow State University(ロシア連邦)

    • Related Report
      2020 Research-status Report
  • [Journal Article] Single-Molecule Magnets Based on Heteroleptic Terbium(III) Trisphthalocyaninate in Solvent-Free and Solvent-Containing Forms2023

    • Author(s)
      Faraonov Maxim A., Martynov Alexander G., Polovkova Marina A., Khasanov Salavat S., Gorbunova Yulia G., Tsivadze Aslan Yu., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V.
    • Journal Title

      Magnetochemistry

      Volume: 9 Issue: 2 Pages: 36-36

    • DOI

      10.3390/magnetochemistry9020036

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] A dimer of the negatively charged carbonyl cluster {Ir4(CO)11-}2 bonded by a single Ir-Ir bond, and comparison with the singly bonded (C60-)2 dimer.2023

    • Author(s)
      Sobov Pavel A., Shestakov Alexander F., Kuzmin Alexey V., Khasanov Salavat S., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V.
    • Journal Title

      Zeitschrift fur anorganische und allgemeine Chemie

      Volume: 649 Issue: 6-7

    • DOI

      10.1002/zaac.202200368

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Binuclear coordination complex of open merocyanine form of photochromic spiropyran with MnII (hfac)2 having high spin (S = 5) ground state2023

    • Author(s)
      Osipov Nikita G., Faraonov Maxim A., Shestakov Alexander F., Mikhailenko Maxim V., Kuzmin Alexey V., Khasanov Salavat S., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V.
    • Journal Title

      New Journal of Chemistry

      Volume: 47 Issue: 11 Pages: 5470-5476

    • DOI

      10.1039/d3nj00058c

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Heterotrimetallic paramagnetic complex of ring reduced tin(II) hexadecachlorophthalocyanine2023

    • Author(s)
      Romanenko Nikita R., Faraonov Maxim A., Osipov Nikita G., Kuzmin Alexey V., Khasanov Salavat S., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V.
    • Journal Title

      New Journal of Chemistry

      Volume: 47 Issue: 14 Pages: 6924-6931

    • DOI

      10.1039/d3nj00506b

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Weak Antiferromagnetic Exchange and Ferromagnetic Alignment of FeII (S=2) Spins in Differently Charged {HAT・(FeIICl2)3}n (n = 2- and 3-) Assemblies of Hexaazatriphenylenes (HAT)2022

    • Author(s)
      Mikhailenko Maxim V., Khasanov Salavat S., Shestakov Alexader F., Kuzmin Aleksey V., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V.
    • Journal Title

      Chemistry - A European Journal

      Volume: 28 Issue: 10

    • DOI

      10.1002/chem.202104165

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Trinuclear coordination assemblies of low-spin dicyano manganese(II) (S = 1/2) and iron(II) (S = 0) phthalocyanines with manganese(II) acetylacetonate, tris(cyclopentadienyl)gadolinium(III) and neodymium(III)2022

    • Author(s)
      Romanenko Nikita R., Kuzmin Alexey V., Mikhailenko Maxim V., Faraonov Maxim A., Khasanov Salavat S., Yudanova Evgeniya I., Shestakov Alexander F., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V.
    • Journal Title

      Dalton Transactions

      Volume: 51 Issue: 25 Pages: 9770-9779

    • DOI

      10.1039/d2dt01052f

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] New HATNA(CN)6 ligand in the design of dianion magnetic assemblies with lanthanides {Cryptand(K+)}2{HATNA(CN)6・3LnIII(TMHD)3}2- (Ln = Gd, Tb and Dy)2022

    • Author(s)
      Mikhailenko Maxim V., Ivanov Vladislav V., Kuzmin Alexey V., Faraonov Maxim A., Shestakov Alexander F., Khasanov Salavat S., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V.
    • Journal Title

      Polyhedron

      Volume: 228 Pages: 116186-116186

    • DOI

      10.1016/j.poly.2022.116186

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Crystalline paramagnetic supramolecular 2D-polymer of the tetra(4-pyridyl)porphyrin and terbium(III) complex2022

    • Author(s)
      Nazarov Dmitry I., Faraonov Maxim A., Kuzmin Alexey V., Khasanov Salavat S., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V.
    • Journal Title

      Dalton Transactions

      Volume: 51 Issue: 44 Pages: 16921-16925

    • DOI

      10.1039/d2dt03170a

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Negatively Charged Iron-Bridged Fullerene Dimer {Fe(CO)2-μ2-η2,η2-C60}2 2-2022

    • Author(s)
      Faraonov Maxim A., Kuzmin Alexey V., Khasanov Salavat S., Shestakov Alexander F., Otsuka Akihiro, Yamochi Hideki, Kitagawa Hiroshi, Konarev Dmitri V.
    • Journal Title

      Inorganic Chemistry

      Volume: 61 Issue: 49 Pages: 20144-20149

    • DOI

      10.1021/acs.inorgchem.2c03595

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Complexes of transition metal carbonyl clusters with tin(II) phthalocyanine in neutral and radical anion states: methods of synthesis, structures and properties2022

    • Author(s)
      Romanenko Nikita R.、Kuzmin Alexey V.、Khasanov Salavat S.、Faraonov Maxim A.、Yudanova Evgeniya I.、Nakano Yoshiaki、Otsuka Akihiro、Yamochi Hideki、Kitagawa Hiroshi、Konarev Dmitri V.
    • Journal Title

      Dalton Transactions

      Volume: 51 Issue: 6 Pages: 2226-2237

    • DOI

      10.1039/d1dt04061h

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Metallic Conduction and Carrier Localization in Two-Dimensional BEDO-TTF Charge-Transfer Solid Crystals2021

    • Author(s)
      Ito Hiroshi、Matsuno Motoki、Katagiri Seiu、Yoshina Shinji K.、Takenobu Taishi、Ishikawa Manabu、Otsuka Akihiro、Yamochi Hideki、Yoshida Yukihiro、Saito Gunzi、Shen Yongbing、Yamashita Masahiro
    • Journal Title

      Crystals

      Volume: 12 Issue: 1 Pages: 23-23

    • DOI

      10.3390/cryst12010023

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Macrocycle- and metal-centered reduction of metal tetraphenylporphyrins where the metal is copper(<scp>ii</scp>), nickel(<scp>ii</scp>) and iron(<scp>ii</scp>)2021

    • Author(s)
      Nazarov Dmitry I.、Andronov Mikhail G.、Kuzmin Aleksey V.、Khasanov Salavat S.、Yudanova Evgeniya I.、Shestakov Alexander F.、Otsuka Akihiro、Yamochi Hideki、Kitagawa Hiroshi、Konarev Dmitri V.
    • Journal Title

      Dalton Transactions

      Volume: 50 Issue: 43 Pages: 15620-15632

    • DOI

      10.1039/d1dt02573b

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M<sup>II</sup><sub>3</sub>O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet?Quartet Transitions in the Dianions2021

    • Author(s)
      Nazarov Dmitry I.、Islyaikin Mikhail K.、Ivanov Evgenii N.、Koifman Oskar I.、Batov Mikhail S.、Zorina Leokadiya V.、Khasanov Salavat S.、Shestakov Alexander F.、Yudanova Evgeniya I.、Zhabanov Yuriy A.、Vyalkin Dmitriy A.、Otsuka Akihiro、Yamochi Hideki、Kitagawa Hiroshi、Torres Tomas、Konarev Dmitri V.
    • Journal Title

      Inorganic Chemistry

      Volume: 60 Issue: 13 Pages: 9857-9868

    • DOI

      10.1021/acs.inorgchem.1c01132

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Emergence of Metallic Conduction and Cobalt(II)-Based Single-Molecule Magnetism in the Same Temperature Range2021

    • Author(s)
      Shen Yongbing、Ito Hiroshi、Zhang Haitao、Yamochi Hideki、Cosquer Goulven、Herrmann Carmen、Ina Toshiaki、Yoshina Shinji K.、Breedlove Brian K.、Otsuka Akihiro、Ishikawa Manabu、Yoshida Takefumi、Yamashita Masahiro
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 13 Pages: 4891-4895

    • DOI

      10.1021/jacs.1c00455

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Effect of reduction on the molecular structure and optical and magnetic properties of fluorinated copper(ii) phthalocyanines2020

    • Author(s)
      Konarev Dmitri V.、Faraonov Maxim A.、Batov Mikhail S.、Andronov Mikhail G.、Kuzmin Alexey V.、Khasanov Salavat S.、Otsuka Akihiro、Yamochi Hideki、Kitagawa Hiroshi、Lyubovskaya Rimma N.
    • Journal Title

      Dalton Transactions

      Volume: 49 Issue: 46 Pages: 16821-16829

    • DOI

      10.1039/d0dt02635b

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Solid‐State Properties of Hexaazatriphenylenehexacarbonitrile HAT(CN)6.- Radical Anions in Crystalline Salts Containing Cryptand(M+) and Crystal Violet Cations2020

    • Author(s)
      Konarev Dmitri V.、Khasanov Salavat S.、Kuzmin Alexey V.、Mikhailenko Maxim V.、Otsuka Akihiro、Yamochi Hideki、Kitagawa Hiroshi、Lyubovskaya Rimma N.
    • Journal Title

      Chemistry A European Journal

      Volume: 26 Issue: 72 Pages: 17470-17480

    • DOI

      10.1002/chem.202002967

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] 有機導体(EDO-TTF-I)2ClO4 の第一原理計算と秩序状態の解析2023

    • Author(s)
      川村 泰喜, 橋本 顕一郎, 吉見 一慶, 石川 学, 中野 義明, 大塚 晃弘, 矢持 秀起, 小林 晃人
    • Organizer
      日本物理学会2023年春季大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] モノアルキル化DABCOとTCNQ誘導体から成るラジカルアニオン塩の構造と物性2021

    • Author(s)
      小川 凌平, 石田 耕大, 岡本 尚大, 石川 学, 中野 義明, 大塚 晃弘, 矢持 秀起
    • Organizer
      第15回 分子科学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] N-アルキル化 DABCOを対カチオンとする TCNQ誘導体のラジカルアニオン塩の構造と物性2021

    • Author(s)
      小川 凌平, 石田 耕大, 石川 学, 岡本 尚大, 中野 義明, 大塚 晃弘, 矢持 秀起
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report

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Published: 2020-04-28   Modified: 2024-01-30  

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