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非対称配位圏がもたらす金属錯体の光新機能:共同研究による配位アシンメトリの推進

Publicly Offered Research

Project AreaCoordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
Project/Area Number 19H04562
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionTohoku University (2020)
Kyoto University (2019)

Principal Investigator

坂本 良太  東北大学, 理学研究科, 教授 (80453843)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2020: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Fiscal Year 2019: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywords金属錯体 / ナノシート / ナノワイヤ / テルピリジン / ジピリン / 非対称金属錯体 / ジチオレン / 配位アシンメトリ
Outline of Research at the Start

対称配位圏を有する錯体モチーフを非対称化することで機能性の向上を図る戦略は, シンプルながらも極めて有効である. 本研究課題では, 上記戦略に基づき, 同時に過去2年間の公募研究の成果を更に発展させることで,「配位アシンメトリ」の概念に即した独創的・革新的な光機能分子材料を創製する.

Outline of Annual Research Achievements

グラッシーカーボン上に共有結合で固定化されたアゾベンゼン架橋ビス(テルピリジン)金属ユニットからなるπ共役酸化還元金属錯体線形ポリマーワイヤを合成する効率的で便利な電気化学的方法を開発した。重合は、水-アセトニトリル-過塩素酸溶液中でビス(4′-(4-アニリノ)-2,2′:6′,2″-テルピリジン)金属錯体の、グラッシーカーボンを作用極とした電気化学的酸化によって進み、最大7400mer(約15μmに相当)のポリマーを得ることに成功した。中心金属として鉄およびルテニウムを有するワイヤは共に可逆的な酸化還元反応を起こし、その酸化還元挙動は極めて速い酸化還元伝導を示した。段階的な電解重合により、FeとRuを中心とする異方性ヘテロ金属錯体ポリマーワイヤが構築された。2つのヘテロ金属錯体ポリマーワイヤはサイクリックボルタンめとりーにおいて、正反対の不可逆なレドックス応答を示したことから、レドックスダイオード特性を有することが分かった。本電気化学的手法は、ポリマーワイヤーアレイの合成や、機能性分子のカーボン上への集積に有用であるとともに、非対称性がこのレドックスダイオード特性の発現に寄与している。この他、水素発生助触媒として機能する金属錯体ナノシート、エレクトロクロミック特性を示す金属錯体ナノシート、トポロジカル絶縁体候補となる金属錯体ナノシート、d10-d10相互作用を示す金/水銀錯体、クリック反応に基づく共有結合ナノシートの構築、を報告した。

Research Progress Status

令和2年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和2年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • Research Products

    (23 results)

All 2022 2021 2020 2019 Other

All Int'l Joint Research (5 results) Journal Article (9 results) (of which Int'l Joint Research: 6 results,  Peer Reviewed: 9 results,  Open Access: 3 results) Presentation (5 results) (of which Int'l Joint Research: 1 results,  Invited: 5 results) Book (4 results)

  • [Int'l Joint Research] Universidad Autonoma de Madrid(スペイン)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] CNRS(フランス)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] Hong Kong Polytechnic University(中国)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] Universitaet Bremen(ドイツ)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] CNRS(フランス)

    • Related Report
      2019 Annual Research Report
  • [Journal Article] Two-Dimensional Metal?Organic Framework Acts as a Hydrogen Evolution Cocatalyst for Overall Photocatalytic Water Splitting2022

    • Author(s)
      Guan Jingyan、Pal Tigmansu、Kamiya Kazuhide、Fukui Naoya、Maeda Hiroaki、Sato Tetsu、Suzuki Hajime、Tomita Osamu、Nishihara Hiroshi、Abe Ryu、Sakamoto Ryota
    • Journal Title

      ACS Catalysis

      Volume: 12 Issue: 7 Pages: 3881-3889

    • DOI

      10.1021/acscatal.1c05889

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Layered metal-organic frameworks and metal-organic nanosheets as functional materials2022

    • Author(s)
      Sakamoto Ryota、Fukui Naoya、Maeda Hiroaki、Toyoda Ryojun、Takaishi Shinya、Tanabe Tappei、Komeda Joe、Amo-Ochoa Pilar、Zamora Felix、Nishihara Hiroshi
    • Journal Title

      Coordination Chemistry Reviews

      Volume: 472 Pages: 214787-214787

    • DOI

      10.1016/j.ccr.2022.214787

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Coordination chemistry for innovative carbon-related materials2022

    • Author(s)
      Sakamoto Ryota、Toyoda Ryojun、Jingyan Guan、Nishina Yuta、Kamiya Kazuhide、Nishihara Hirotomo、Ogoshi Tomoki
    • Journal Title

      Coordination Chemistry Reviews

      Volume: 466 Pages: 214577-214577

    • DOI

      10.1016/j.ccr.2022.214577

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Ultralong π-Conjugated Bis(terpyridine)metal Polymer Wires Covalently Bound to a Carbon Electrode: Fast Redox Conduction and Redox Diode Characteristics2021

    • Author(s)
      K.-H. Wu, R. Sakamoto, H. Maeda, E. J. H. Phua, H. Nishihara
    • Journal Title

      MOLECULES

      Volume: 26 Issue: 14 Pages: 4267-4267

    • DOI

      10.3390/molecules26144267

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] ’Click’ conjugated porous polymer nanofilm with a large domain size created by a liquid/liquid interfacial protocol2020

    • Author(s)
      J. Komeda, R. Shiotsuki, A. Rapakousiou, R. Sakamoto, R. Toyoda, K. Iwase, M. Tsuji, K. Kamiya, H. Nishihara
    • Journal Title

      Chem. Commun.

      Volume: 56 Issue: 25 Pages: 3677-3680

    • DOI

      10.1039/d0cc00360c

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Carbon-rich materials with three-dimensional ordering at the angstrom level2020

    • Author(s)
      Fa Shixin、Yamamoto Masanori、Nishihara Hirotomo、Sakamoto Ryota、Kamiya Kazuhide、Nishina Yuta、Ogoshi Tomoki
    • Journal Title

      Chemical Science

      Volume: 11 Issue: 23 Pages: 5866-5873

    • DOI

      10.1039/d0sc02422h

    • NAID

      120006958098

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Interfacial Transmetallation Synthesis of Platinadithiolene Nanosheet as a Potential 2D Topological Insulator2019

    • Author(s)
      T. Pal, S. Doi, H. Maeda, K. Wada, C. M. Tan, N. Fukui, R. Sakamoto, S. Tsuneyuki, S. Sasaki, H. Nishihara
    • Journal Title

      Chem. Sci.

      Volume: 10 Issue: 20 Pages: 5218-5225

    • DOI

      10.1039/c9sc01144g

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Electrochromic triphenylamine-based cobalt(II) complex nanosheets2019

    • Author(s)
      Y. Liu, R. Sakamoto, C.-H. Ho, H. Nishihara, W.-Y. R. Wong
    • Journal Title

      J. Mater. Chem. C

      Volume: 7 Issue: 30 Pages: 9159-9166

    • DOI

      10.1039/c9tc02257k

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d <sup>10</sup> ?d <sup>10</sup> Interactions2019

    • Author(s)
      Olaru Marian、K?gel Julius F.、Aoki Risa、Sakamoto Ryota、Nishihara Hiroshi、Lork Enno、Mebs Stefan、Vogt Matthias、Beckmann Jens
    • Journal Title

      Chemistry A European Journal

      Volume: 26 Issue: 1 Pages: 275-284

    • DOI

      10.1002/chem.201904106

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] 分子性ナノシート・ナノワイヤの新展開2021

    • Author(s)
      坂本 良太
    • Organizer
      第245 回有機エレクトロニクス材料研究会 「トポロジカル絶縁体」
    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Invited
  • [Presentation] Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface2020

    • Author(s)
      Ryota Sakamoto
    • Organizer
      Pure and Applied Chemistry International Conference
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 分子低次元物質の新展開2020

    • Author(s)
      坂本 良太
    • Organizer
      CEMS Topical Meeting Onlineー 超分子ポリマーの進化形 ー
    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Invited
  • [Presentation] 光機能性ナノワイヤ・ナノシート2019

    • Author(s)
      坂本 良太
    • Organizer
      第68回高分子討論会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 新規ナノカーボン「グラフィジイン」の精密合成2019

    • Author(s)
      坂本 良太
    • Organizer
      第46回炭素材料学会年会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Book] Functional Nanomaterials: Synthesis, Properties, and Applications2022

    • Author(s)
      Ryota Sakamoto (Eds. W.-Y. Wong and Q. Dong)
    • Total Pages
      560
    • Publisher
      WILEY-VCH
    • ISBN
      9783527828555
    • Related Report
      2020 Annual Research Report
  • [Book] Functional Nanomaterials. Synthesis, Properties and Applications2022

    • Author(s)
      Eds. W.-Y. Wong and Q. Dong
    • Total Pages
      500
    • Publisher
      WILEY-VCH
    • Related Report
      2019 Annual Research Report
  • [Book] ポストグラフェン材料の創製と用途開発最前線2020

    • Author(s)
      坂本 良太(柚原 淳司 監修)
    • Total Pages
      448
    • Publisher
      エヌ・ティー・エス
    • ISBN
      9784860436575
    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
  • [Book] グラフェンから広がる二次元物質の新技術と応用2020

    • Author(s)
      坂本 良太(吾郷 浩樹、齋藤理一郎 監修)
    • Total Pages
      558
    • Publisher
      エヌ・ティー・エス
    • ISBN
      9784860436636
    • Related Report
      2020 Annual Research Report 2019 Annual Research Report

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Published: 2019-04-18   Modified: 2023-12-25  

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