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Hydride-doped gold clusters: elucidation of their formation mechanisms and reactivities

Research Project

Project/Area Number 19K15499
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 32010:Fundamental physical chemistry-related
Research InstitutionThe University of Tokyo

Principal Investigator

Takano Shinjiro  東京大学, 大学院理学系研究科(理学部), 助教 (40783957)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2019: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywords配位子保護金超原子 / 配位子保護金クラスター / 配位子保護合金クラスター / 金超原子
Outline of Research at the Start

申請者は最近、配位子によって保護された金クラスターに対して結合したヒドリド(H-)が幾何・電子的にあたかも金原子のように振る舞うことを見出し、”ヒドリドドープ”という新概念を提案した。本研究課題では、この新概念の一般性を検証するとともに、ヒドリドドーピングによる金クラスターの電子的活性化を生かした新しいクラスター転換反応を開拓することを目的とする。本研究を通して、ヒドリドをドーパントとする新しい合金クラスターを創出し、さらにその化学特性を生かした新規クラスター化合物のボトムアップ合成法を開発することで、ナノ化学の進展に貢献する。

Outline of Final Research Achievements

Gold clusters composed of a few tenth of atoms are isolatable chemical compounds when they are protected by organic ligands. Their novel size-dependent properties enable us to utilize them as a new class of functional materials at the nanoscale.
In this research project, the properties and reactivities of novel hydrogen-containing gold clusters have been investigated in detail. The findings enable us to systematically synthesize a variety of gold clusters with reproducible manner and to investigate the fundamental properties of gold clusters.

Academic Significance and Societal Importance of the Research Achievements

本研究の遂行により、これまで少数の研究者のみが合成可能であったいくつかの合金クラスターを再現性および収率・収量の面から凌駕する合成法を確立し、その基礎物性を明らかにできた。加えて、ほぼ偶然に頼らざるを得なかったクラスターの選択的合成も達成し、その興味深い特性も明らかにした。
これらの結果は、配位子保護金クラスターの基礎的な理解を深化する重要な結果であり、それを基にした光エネルギー変換や触媒研究等の応用研究へ重要な知見を与えると考えられる。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (12 results)

All 2021 2020 2019

All Journal Article (8 results) (of which Peer Reviewed: 7 results) Presentation (4 results) (of which Int'l Joint Research: 1 results,  Invited: 1 results)

  • [Journal Article] Chemically Modified Gold/Silver Superatoms as Artificial Elements at Nanoscale: Design Principles and Synthesis Challenges2021

    • Author(s)
      Takano Shinjiro、Tsukuda Tatsuya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 4 Pages: 1683-1698

    • DOI

      10.1021/jacs.0c11465

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Controlled Dimerization and Bonding Scheme of Icosahedral M@Au12 (M=Pd, Pt) Superatoms2020

    • Author(s)
      Ito Emi、Takano Shinjiro、Nakamura Toshikazu、Tsukuda Tatsuya
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 2 Pages: 645-649

    • DOI

      10.1002/anie.202010342

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Understanding Doping Effects on Electronic Structures of Gold Superatoms: A Case Study of Diphosphine-Protected M@Au12 (M = Au, Pt, Ir)2020

    • Author(s)
      Hirai Haru、Takano Shinjiro、Nakamura Toshikazu、Tsukuda Tatsuya
    • Journal Title

      Inorganic Chemistry

      Volume: 59 Issue: 24 Pages: 17889-17895

    • DOI

      10.1021/acs.inorgchem.0c00879

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synergistic Effects of Pt and Cd Codoping to Icosahedral Au13 Superatoms2020

    • Author(s)
      Suyama Megumi、Takano Shinjiro、Tsukuda Tatsuya
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Issue: 43 Pages: 23923-23929

    • DOI

      10.1021/acs.jpcc.0c06765

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Stoichiometric Formation of Open-Shell [PtAu24(SC2H4Ph)18]- via Spontaneous Electron Proportionation between [PtAu24(SC2H4Ph)18]2- and [PtAu24(SC2H4Ph)18]02019

    • Author(s)
      Suyama Megumi、Takano Shinjiro、Nakamura Toshikazu、Tsukuda Tatsuya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 36 Pages: 14048-14051

    • DOI

      10.1021/jacs.9b06254

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Efficient and Selective Conversion of Phosphine-Protected (MAu8)2+ (M = Pd, Pt) Superatoms to Thiolate-Protected (MAu12)6+ or Alkynyl-Protected (MAu12)4+ Superatoms via Hydride Doping2019

    • Author(s)
      Takano Shinjiro、Ito Shun、Tsukuda Tatsuya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 40 Pages: 15994-16002

    • DOI

      10.1021/jacs.9b08055

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Alkynyl-Protected Au22(C≡CR)18 Clusters Featuring New Interfacial Motifs and R-Dependent Photoluminescence2019

    • Author(s)
      Ito Shun、Takano Shinjiro、Tsukuda Tatsuya
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 10 Issue: 21 Pages: 6892-6896

    • DOI

      10.1021/acs.jpclett.9b02920

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] クラスター間の自発的電子移動による開殼系クラスター[PtAu24(SC2H4Ph)18]-の化学量論的生成2019

    • Author(s)
      陶山 めぐみ , 高野 慎二郎 , 中村 敏和 , 佃 達哉
    • Journal Title

      ナノ学会会報 = The bulletin of the Society of Nano Science and Technology

      Volume: 18 Pages: 21-26

    • Related Report
      2019 Research-status Report
  • [Presentation] Development of precise transformation reactions of gold superatoms initiated by hydride doping2020

    • Author(s)
      Shinjiro Takano, Shun Ito, Tatsuya Tsukuda
    • Organizer
      日本化学会第100回春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Hydride-Doped Gold Clusters: Syntheses, Structures, and Transforamtions2019

    • Author(s)
      Shinjiro Takano and Tatsuya Tsukuda
    • Organizer
      The 76th Fujihara Seminar International Workshop on Designer Nanocluster Materials - From Gas Phase to Condensed Phase -
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] ヒドリドドープ金超原子を利用した精密変換反応の開発2019

    • Author(s)
      高野慎二郎,伊藤駿, 佃達哉
    • Organizer
      第13回分子科学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] ヒドリドドーピングを鍵とする金超原子の精密変換反応の開拓:表面化学修飾2019

    • Author(s)
      高野慎二郎,伊藤駿, 佃達哉
    • Organizer
      ナノ学会第17回大会
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2022-01-27  

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