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Isotope recognition of hydrogen ions using the inner space of multinuclear metal complexes

Research Project

Project/Area Number 20K21209
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 InstitutionOsaka University

Principal Investigator

Masaoka Shigeyuki  大阪大学, 工学研究科, 教授 (20404048)

Project Period (FY) 2020-07-30 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2021: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Fiscal Year 2020: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywords錯体化学 / 多核金属錯体 / 水素イオン / 分子認識 / 水素イオン同位体
Outline of Research at the Start

本研究では、多核金属錯体を利用した水素イオンの同位体認識を目標とした研究を展開する。具体的には、ホスト骨格となる多核金属錯体内の小空間のサイズ・構造を緻密に制御し、各同位体に適した認識場を構築する。得られたホスト分子を用いて望みの同位体イオンを選択的に空間中に捕捉した後、電気化学的刺激によりホスト外へと放出させる。これらのプロセスにより、極めて温和な条件で簡便に水素同位体を高効率に分離・精製可能なシステムが構築される。本提案は申請者のこれまでの研究知見に基づき立案された挑戦的かつ革新的な研究課題であり、類似の着想に基づく研究例は皆無である。

Outline of Final Research Achievements

In host-guest chemistry, protons, which are involved in the functionalization of a substance, are considered to be interesting guests, and their capture in a small space is expected to lead to specific behavior and new functionalities. The aim of this study was to develop research aimed at the creation of new host compounds by utilizing a pentanuclear complex consisting of five metal ions and multinucleating ligands. As a specific research result, a rational synthetic method for heterometallic pentanuclear complexes as host compounds was first established. Furthermore, the electron transfer behavior of the resulting heterometallic pentanuclear complexes was elucidated. Finally, the influence of the protons encapsulated in the heterometallic pentanuclear complexes on their physical properties and functions was also successfully evaluated.

Academic Significance and Societal Importance of the Research Achievements

本研究により、異種金属5核錯体内部の小空間にプロトンを内包させることに成功し、また内包されたプロトンが新奇な刺激応答性を示すことが判明した。この内包プロトンが示す挙動は、従来型の酸―塩基理論では解釈できないものであり、空間的に孤立したプロトンの特異性が示された。すなわち、本研究では従来の概念を打ち破る新たな物質群の創出を達成したと言える。更に、内包プロトンの有無により異種金属5核錯体の物性ならびに水素発生反応に対する触媒機能が大きく変化することも見出され、内包プロトンの重要性が示された。以上の通り本研究は、プロトンを対象としたホスト―ゲスト化学に新たな知見をもたらすものである。

Report

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

    (22 results)

All 2022 2021 2020

All Journal Article (12 results) (of which Peer Reviewed: 12 results,  Open Access: 2 results) Presentation (7 results) (of which Int'l Joint Research: 2 results,  Invited: 7 results) Book (3 results)

  • [Journal Article] Copper(II) tetrakis(pentafluorophenyl)porphyrin: highly active copper-based molecular catalysts for electrochemical CO2 reduction2022

    • Author(s)
      Kosugi Kento、Kashima Hina、Kondo Mio、Masaoka Shigeyuki
    • Journal Title

      Chemical Communications

      Volume: 58 Issue: 18 Pages: 2975-2978

    • DOI

      10.1039/d1cc05880k

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photochemical hydrogen production based on the HCOOH/CO2 cycle promoted by a pentanuclear cobalt complex2022

    • Author(s)
      Akai Takuya、Kondo Mio、Saga Yutaka、Masaoka Shigeyuki
    • Journal Title

      Chemical Communications

      Volume: 58 Issue: 23 Pages: 3755-3758

    • DOI

      10.1039/d1cc06445b

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Electrochemical Polymerization of a Carbazole‐Tethered Cobalt Phthalocyanine for Electrocatalytic Water Oxidation2022

    • Author(s)
      Li Shangxing、Iwami Hikaru、Kondo Mio、Masaoka Shigeyuki
    • Journal Title

      ChemNanoMat

      Volume: in press. Issue: 6

    • DOI

      10.1002/cnma.202200028

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visible light-driven CO2 reduction with a Ru polypyridyl complex bearing an N-heterocyclic carbene moiety2022

    • Author(s)
      Watanabe Taito、Saga Yutaka、Kosugi Kento、Iwami Hikaru、Kondo Mio、Masaoka Shigeyuki
    • Journal Title

      Chemical Communications

      Volume: 58 Issue: 34 Pages: 5229-5232

    • DOI

      10.1039/d2cc00657j

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Design of molecular water oxidation catalysts with earth-abundant metal ions2021

    • Author(s)
      Kondo Mio、Tatewaki Hayato、Masaoka Shigeyuki
    • Journal Title

      Chemical Society Reviews

      Volume: 50 Issue: 12 Pages: 6790-6831

    • DOI

      10.1039/d0cs01442g

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photoconductive Coordination Polymer with a Lead-Sulfur Two-Dimensional Coordination Sheet Structure2021

    • Author(s)
      Kamakura Yoshinobu、Sakura Chinatsu、Saeki Akinori、Masaoka Shigeyuki、Fukui Akito、Kiriya Daisuke、Ogasawara Kazuyoshi、Yoshikawa Hirofumi、Tanaka Daisuke
    • Journal Title

      Inorganic Chemistry

      Volume: 60 Issue: 8 Pages: 5436-5441

    • DOI

      10.1021/acs.inorgchem.0c03801

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dirhodium-Based Supramolecular Framework Catalyst for Visible-Light-Driven Hydrogen Evolution2021

    • Author(s)
      Chinapang Pondchanok、Iwami Hikaru、Enomoto Takafumi、Akai Takuya、Kondo Mio、Masaoka Shigeyuki
    • Journal Title

      Inorganic Chemistry

      Volume: 60 Issue: 17 Pages: 12634-12643

    • DOI

      10.1021/acs.inorgchem.1c01279

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Quick and Easy Method to Dramatically Improve the Electrochemical CO2 Reduction Activity of an Iron Porphyrin Complex2021

    • Author(s)
      Kosugi Kento、Kondo Mio、Masaoka Shigeyuki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 40 Pages: 22070-22074

    • DOI

      10.1002/anie.202110190

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Fabrication of a Function‐Integrated Water Oxidation Catalyst through the Electrochemical Polymerization of Ruthenium Complexes2021

    • Author(s)
      Iwami Hikaru、Kondo Mio、Masaoka Shigeyuki
    • Journal Title

      ChemElectroChem

      Volume: 9 Issue: 2 Pages: 52-58

    • DOI

      10.1002/celc.202101363

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Electrochemical Polymerization Provides a Function‐Integrated System for Water Oxidation2021

    • Author(s)
      Iwami Hikaru、Okamura Masaya、Kondo Mio、Masaoka Shigeyuki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 11 Pages: 5965-5969

    • DOI

      10.1002/anie.202015174

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Modulation of Self‐Assembly Enhances the Catalytic Activity of Iron Porphyrin for CO 2 Reduction2021

    • Author(s)
      Tasaki Masahiro、Okabe Yuki、Iwami Hikaru、Akatsuka Chiharu、Kosugi Kento、Negita Kohei、Kusaka Sinpei、Matsuda Ryotaro、Kondo Mio、Masaoka Shigeyuki
    • Journal Title

      Small

      Volume: in press Issue: 22 Pages: 2006150-2006150

    • DOI

      10.1002/smll.202006150

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Pentanuclear Scaffold: A Molecular Platform for Small-Molecule Conversions2020

    • Author(s)
      Kondo Mio、Masaoka Shigeyuki
    • Journal Title

      Accounts of Chemical Research

      Volume: 53 Issue: 10 Pages: 2140-2151

    • DOI

      10.1021/acs.accounts.0c00186

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Presentation] Development of molecular catalysts for artificial photosynthesis, Shigeyuki Masaoka2021

    • Author(s)
      Shigeyuki Masaoka
    • Organizer
      SJTU and OU Joint Workshop on Organic Chemistry
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 人工光合成への挑戦~空気や水から価値ある分子を~2021

    • Author(s)
      正岡重行
    • Organizer
      第130回 分子科学フォーラム
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 金属錯体で創造する光合成反応触媒2021

    • Author(s)
      正岡重行
    • Organizer
      カーボンニュートラル社会の実現に向けた触媒科学の挑戦, 大阪大学ICS-OTRI触媒科学シンポジウム
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 金属錯体の電子移動制御に立脚した触媒開発2021

    • Author(s)
      正岡重行
    • Organizer
      早稲田大学講演会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] Molecular Catalysts for Artificial Photosynthesis2021

    • Author(s)
      Shigeyuki Masaoka
    • Organizer
      Chemical Approaches for Sustainable Development Goals (SDGs), Osaka University Anniversary Lecture Series1
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 小分子の多電子酸化/還元反応のための多核金属錯体触媒2020

    • Author(s)
      正岡 重行
    • Organizer
      新学術領域「ハイブリッド触媒」第4回公開シンポジウム
    • Related Report
      2020 Research-status Report
    • Invited
  • [Presentation] 金属錯体の電子移動制御に立脚した触媒開発2020

    • Author(s)
      正岡 重行
    • Organizer
      福岡大学セミナー
    • Related Report
      2020 Research-status Report
    • Invited
  • [Book] 生命金属ダイナミクス2021

    • Author(s)
      近藤美欧, 正岡重行
    • Total Pages
      564
    • Publisher
      エヌ・ティー・エス
    • ISBN
      9784860437060
    • Related Report
      2020 Research-status Report
  • [Book] 高機能性金属錯体が拓く触媒科学2020

    • Author(s)
      近藤美欧, 正岡重行
    • Total Pages
      224
    • Publisher
      化学同人
    • ISBN
      9784759813975
    • Related Report
      2020 Research-status Report
  • [Book] 光エネルギー変換における分子触媒の新展開2020

    • Author(s)
      近藤美欧, 正岡重行
    • Total Pages
      224
    • Publisher
      化学同人
    • ISBN
      9784759813982
    • Related Report
      2020 Research-status Report

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Published: 2020-08-03   Modified: 2023-01-30  

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