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Syntheses of Porous Molecular Conductors toward Creating and Controlling Novel Electronic States

Research Project

Project/Area Number 21H01901
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 32020:Functional solid state chemistry-related
Research InstitutionNagoya University (2022-2023)
Tohoku University (2021)

Principal Investigator

Iguchi Hiroaki  名古屋大学, 工学研究科, 准教授 (30709100)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000)
Fiscal Year 2023: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2022: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2021: ¥11,570,000 (Direct Cost: ¥8,900,000、Indirect Cost: ¥2,670,000)
Keywords多孔性配位高分子(MOF) / 分子性導体 / 一次元電子系 / 電気伝導 / ナフタレンジイミド / ドーピング / 分子性量子ビット(Qbit) / マクロサイクル / インドロカルバゾール / ガスセンサー / ホストーゲスト相互作用 / 化学ドーピング / 多孔性配位高分子 / ホスト-ゲスト相互作用
Outline of Research at the Start

新奇な電子状態の発見は、新しい機能の発現、さらには新たな学問分野の開拓や産業的応用につながることから、電子状態を制御する新たな手法の開発は非常に重要である。本研究では、有機結晶における新しい電子状態開拓法として分子の吸脱着を適用する。そのために、既存の分子性導体と多孔性配位高分子(MOF)の長所を併せ持つ多孔性分子導体(PMC)を開発し、分子の吸脱着に柔軟に応答して構造が可逆的に変化する結晶を合成する。この骨格の構造変化によるバンド構造制御、ナノ細孔に吸着した分子との電荷移動によるバンドフィリング制御を駆使して新奇な電子状態を探索する。

Outline of Final Research Achievements

In this study, we focused on porous molecular conductors (PMCs), which have the characteristics of both molecular conductors and porous coordination polymers, in order to control the electronic states of the entire bulk molecular crystal. We worked on the development of robust PMCs whose crystallinity does not deteriorate even after repeated molecular adsorption and desorption. In addition, their electronic states and electronic properties were controlled by the guest adsorption and desorption.
During the research, we found unexpected functions, such as an unusual blue coloration of the ligand and a π-radical crystal showing slow magnetic relaxation, which is applicable to molecular quantum bits. We synthesized various PMCs in a variety of framework dimensionality from zero to three. Their robustness were improved compared to reported PMCs. We also found changes in electronic structure and physical properties upon reaction with redox-active molecules.

Academic Significance and Societal Importance of the Research Achievements

導電性と多孔性を併せ持つ物質は、電池やスーパーキャパシタの電極材料、分子選択的センサー、電気化学触媒等への応用が期待されている。PMCは結晶性が高く、規則的なナノ細孔構造を有している点や、分子設計によってナノ細孔の大きさや化学機能をチューニング可能な点で、炭素材料に代表される既存の物質系にはない特長を有しており、特に高機能性が求められる局面で有用な導電性多孔質材料となりうる。本研究によって多様なPMCが開発できたことで、今後の応用展開への道が開けた。一方で、化学ドーピングによって自在に電子状態を制御可能になることで、分子性結晶では困難であった新奇な電子状態や電子物性の探索が可能になりつつある。

Report

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

    (30 results)

All 2024 2023 2022 2021

All Journal Article (10 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 10 results,  Open Access: 4 results) Presentation (19 results) (of which Int'l Joint Research: 7 results,  Invited: 12 results) Book (1 results)

  • [Journal Article] Structure and Physical Properties of Alternately Stacked Donor-acceptor Complexes with 5,11-Dimethyl-5,11-dihydroindolo[3,2-b]carbazole2023

    • Author(s)
      Chiba Yuta、Tanabe Tappei、Koyama Shohei、Yamanaka Shuntaro、Takaishi Shinya、Sakamoto Ryota、Iguchi Hiroaki
    • Journal Title

      Chemistry Letters

      Volume: 52 Issue: 6 Pages: 488-491

    • DOI

      10.1246/cl.230175

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Hexagonal crystalline Magnus’ green salt analogues prepared from hydroxy-functionalised Pt and Pd complexes2023

    • Author(s)
      Mian Mohammad Rasel、Afrin Unjila、Takaishi Shinya、Breedlove Brian K.、Yamashita Masahiro、Iguchi Hiroaki
    • Journal Title

      Dalton Transactions

      Volume: 52 Issue: 42 Pages: 15503-15509

    • DOI

      10.1039/d3dt01700a

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Observation of slow magnetic relaxation phenomena in spatially isolated π-radical ions2023

    • Author(s)
      Koyama Shohei、Sato Kazunobu、Yamashita Masahiro、Sakamoto Ryota、Iguchi Hiroaki
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 25 Issue: 7 Pages: 5459-5467

    • DOI

      10.1039/d2cp06026d

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Data Mining from XANES Spectra of Nickel Complexes for Structure Estimation2023

    • Author(s)
      Fuku Kentaro、Yoshida Takefumi、Sato Tetsu、Iguchi Hiroaki、Takaishi Shinya、Sakamoto Ryota、Abe Hitoshi
    • Journal Title

      Chemistry Letters

      Volume: 52 Issue: 4 Pages: 289-291

    • DOI

      10.1246/cl.230028

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Deprotonation‐Induced Color Modulation in N,N′‐Dihydroxynaphthalenediimide‐Based Organic Crystals2023

    • Author(s)
      Tanabe Tappei、Sato Tetsu、Fuku Kentaro、Takaishi Shinya、Iguchi Hiroaki
    • Journal Title

      ChemPlusChem

      Volume: - Issue: 7

    • DOI

      10.1002/cplu.202300140

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Benzenetriimide‐Based Molecular Conductor with Antiferro‐ to Ferromagnetic Switching Induced by Structural Change of π‐stacked Array2022

    • Author(s)
      Koyama Shohei、Horii Yoji、Sato Tetsu、Takaishi Shinya、Hoshino Norihisa、Akutagawa Tomoyuki、Iguchi Hiroaki
    • Journal Title

      ChemPhysChem

      Volume: 23 Issue: 19

    • DOI

      10.1002/cphc.202200322

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Orthogonal Grade-Separated Nanowiring of Molecular Single Chains2022

    • Author(s)
      Nakajima Hirotaka、Iguchi Hiroaki、Takaishi Shinya、Sato Tetsu、Breedlove Brian K.、Ishikawa Ryuta、Kawata Satoshi、Wan Qingyun、Wakizaka Masanori、Yamashita Masahiro
    • Journal Title

      Chemistry of Materials

      Volume: 35 Issue: 1 Pages: 116-122

    • DOI

      10.1021/acs.chemmater.2c02720

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] An electrically conductive metallocycle: densely packed molecular hexagons with π-stacked radicals2022

    • Author(s)
      Cui Mengxing、Murase Ryuichi、Shen Yongbing、Sato Tetsu、Koyama Shohei、Uchida Kaiji、Tanabe Tappei、Takaishi Shinya、Yamashita Masahiro、Iguchi Hiroaki
    • Journal Title

      Chemical Science

      Volume: 13 Issue: 17 Pages: 4902-4908

    • DOI

      10.1039/d2sc00447j

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Bluish Hydrochromic Naphthalenediimide Salt: Change of Hydrogen-bond Interactions as the New Mechanism of Vapochromism2021

    • Author(s)
      Tanabe Tappei、Sato Tetsu、Fuku Kentaro、Uchida Kaiji、Yamauchi Tamon、Takaishi Shinya、Iguchi Hiroaki
    • Journal Title

      Chemistry Letters

      Volume: 50 Issue: 8 Pages: 1479-1482

    • DOI

      10.1246/cl.210275

    • NAID

      130008072825

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Interdigitated Pt?Br chains with π-stacking: an approach toward Robin?Day class I mixed valency in MX-chain complexes2021

    • Author(s)
      Afrin Unjila、Fuku Kentaro、Cui Mengxing、Iguchi Hiroaki、Mian Mohammad Rasel、Nakanishi Ryo、Takaishi Shinya、Yamashita Masahiro
    • Journal Title

      Dalton Transactions

      Volume: 50 Issue: 40 Pages: 14125-14129

    • DOI

      10.1039/d1dt02996g

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] ナノ細孔とπ積層骨格を併せ持つ導電性配位高分子の開発2024

    • Author(s)
      井口弘章、Qu Liyuan、田邉辰平
    • Organizer
      第6回固体化学フォーラム研究会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 電子状態の自在制御を目指した多孔性分子導体の開発2024

    • Author(s)
      井口弘章
    • Organizer
      日本化学会第104春季年会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] ナノ細孔を有する分子性導体の開発2024

    • Author(s)
      井口弘章
    • Organizer
      ISSPワークショップ「デバイス活用で臨む有機伝導体の未来」
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] Porous Molecular Conductors: Self-Assembly of Coordination Networks by π-Radicals2023

    • Author(s)
      Hiroaki Iguchi
    • Organizer
      4th IRTG Munster-Nagoya Joint Symposium
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Porous Molecular Conductors: Electron-Conductive Coordination Networks Assembled by π-Radicals2023

    • Author(s)
      Hiroaki Iguchi
    • Organizer
      Functional Porous Materials & Reticular Chemistry of Porous Polymers Workshop
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Porous Molecular Conductors Constructed from Naphthalenediimide-based Coordination Networks and Metallocycles2023

    • Author(s)
      Hiroaki Iguchi, Tappei Tanabe, Mengxing Cui, Ryuichi Murase, Liyuan Qu, Shinya Takaishi, Masahiro Yamashita
    • Organizer
      14th Japan-China Joint Symposium on Conduction and Photoconduction in Organic Solids and Related Phenomena
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Controlling Electronic Properties of Coordination Polymers by Guest Desorption2023

    • Author(s)
      Hiroaki Iguchi
    • Organizer
      Mini-Symposium on Innovative Visualization for Materials Science
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 配位結合を用いた多孔性分子導体の開発2023

    • Author(s)
      井口弘章
    • Organizer
      分子系の複合電子機能 第181委員会 最終研究会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] 多孔性分子導体の開発2023

    • Author(s)
      井口弘章
    • Organizer
      錯体物性科学研究会 分子・ナノ・量子が拓く未来材料
    • Related Report
      2022 Annual Research Report
  • [Presentation] 堅牢な多孔性分子導体の開発とゲスト分子による電子物性制御2023

    • Author(s)
      井口弘章
    • Organizer
      2022年度量子ビームサイエンスフェスタ
    • Related Report
      2022 Annual Research Report
  • [Presentation] Electrically conductive metallocycle: densely packed molecular hexagons assembled by π-radicals2022

    • Author(s)
      Hiroaki Iguchi
    • Organizer
      8th Asian Conference on Coordination Chemistry (ACCC8)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Crystal Structure and Conductive Properties of Porous Molecular Conductors2022

    • Author(s)
      Hiroaki Iguchi
    • Organizer
      The 17th Conference of the Asian Crystallographic Association (AsCA2022)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 配位結合で構築する多孔性π積層骨格とその電子物性2022

    • Author(s)
      井口 弘章
    • Organizer
      第3回錯体化学会フロンティアセミナー
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] Design of Electrically Conductive Nanowire Metal Complexes and Porous Molecular Conductors2022

    • Author(s)
      Hiroaki Iguchi
    • Organizer
      Nankai Symposium on Advanced Functional Materials
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ナノサイズの孔を持つ分子性導体を創る2022

    • Author(s)
      井口弘章
    • Organizer
      ITbM/GTRコンソーシアムワークショップ GTR Seeds Seminar
    • Related Report
      2022 Annual Research Report
  • [Presentation] Porous Molecular Conductor Constructed from Densely Packed Hexagonal Metallocycle2022

    • Author(s)
      Hiroaki Iguchi, Mengxing Cui, Ryuichi Murase, Shinya Takaishi, MasahiroYamashita
    • Organizer
      錯体化学会第72回討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 大環状金属錯体が稠密に積層した多孔性分子導体の合成と物性2022

    • Author(s)
      井口弘章、Mengxing Cui、村瀬龍一、Yongbing Shen、佐藤鉄、小山翔平、内田海路、田邉辰平、高石慎也、山下正廣
    • Organizer
      第30回有機結晶シンポジウム
    • Related Report
      2022 Annual Research Report
  • [Presentation] Syntheses and Physical Properties of Robust Porous Molecular Conductors with 1,2,4-Triazole Group2022

    • Author(s)
      Hiroaki Iguchi, Mengxing Cui, Yongbing Shen, Shohei Koyama, Shinya Takaishi
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 多孔性分子導体の開発:現況と問題点2021

    • Author(s)
      井口弘章
    • Organizer
      2021年度物性研究所短期研究会・分子性固体研究の拡がり:新物質と新現象
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Book] 錯体化学会フロンティア選書 フロンティア ナノ金属錯体化学2022

    • Author(s)
      山下正廣, 小西克明 編著
    • Total Pages
      435
    • Publisher
      三共出版
    • ISBN
      9784782708019
    • Related Report
      2022 Annual Research Report

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

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