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2019 Fiscal Year Annual Research Report

超原子および超原子分子の標的合成と機能開拓

Research Project

Project/Area Number 17H01182
Research InstitutionThe University of Tokyo

Principal Investigator

佃 達哉  東京大学, 大学院理学系研究科(理学部), 教授 (90262104)

Project Period (FY) 2017-04-01 – 2020-03-31
Keywords超原子 / 超原子分子
Outline of Annual Research Achievements

本研究では、特異な機能を積極的に付与するという視点から、新奇の超原子および超原子でできた擬似的な分子(超原子分子)の物質科学を切り拓くことを目的としている。最終年度は下記の成果を得た。
【テーマ1】機能性超原子の標的合成と評価
(1) チオラートで保護された金や銀の超原子負イオンに光電子分光法を適用し、ドーピングが電子構造に与える影響を明らかにした他、多価の負イオン種からはクーロン反発ポテンシャルを経た電子脱離や光誘起熱電子放出などユニークな現象を観測した。(2) 高分解能透過型電子顕微鏡を用いて、Au25(SeR)18 の可視化、及びAu144(SR)60においてコアが正二十面体から面心立方格子に異性化する様子を観察した。(3) ヒドリドがドープされた超原子HPdAu8に対してM(I)Cl (M = Ag, Cu)を反応させると、M原子を2個だけ位置選択的に導入した新奇3元超原子HPdAu8M2を得た。一方、HPdAu8にAu(I)L (Lはチオラートあるいはアルキニル配位子)を反応させると、正二十面体のMAu12をコアとするMAu24L18が高効率・高選択的に得られた。(4) N―ヘテロ環状カルベン、あるいはシクロヘキサンチオールで保護した正二十面体構造のAu13超原子の合成に成功した。前者は発光に対して高い量子収率を示し、後者は還元に対して高い耐性を持つ開殻状態で得られた。(5) 閉殻のPtAu12(8e)超原子から半閉殻のPtAu12(6e)への自発的な電子移動によって、開殻のPtAu12(7e)が得られた。
【テーマ2】超原子分子の標的合成と評価
(1) アルキニルで保護されたAu22(C≡CR)18は、双四面体構造のAu7をコアとして持ち、可視発光を示した。(2) HPdAu8を出発物質とする、双二十面体構造のPdMAu21の標的合成に成功した。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

  • Research Products

    (38 results)

All 2020 2019 Other

All Int'l Joint Research (3 results) Journal Article (21 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 21 results,  Open Access: 6 results) Presentation (12 results) (of which Int'l Joint Research: 9 results,  Invited: 12 results) Book (1 results) Remarks (1 results)

  • [Int'l Joint Research] Queen's University(カナダ)

    • Country Name
      CANADA
    • Counterpart Institution
      Queen's University
  • [Int'l Joint Research] University of Jyvaskyla(フィンランド)

    • Country Name
      FINLAND
    • Counterpart Institution
      University of Jyvaskyla
  • [Int'l Joint Research] Pontificia Universidad Catolica de Chile(チリ)

    • Country Name
      CHILE
    • Counterpart Institution
      Pontificia Universidad Catolica de Chile
  • [Journal Article] Base Catalytic Activity of [Nb10O28]6-: Effect of Countercations2020

    • Author(s)
      Hayashi Shun、Yamazoe Seiji、Tsukuda Tatsuya
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Pages: 10975~10980

    • DOI

      10.1021/acs.jpcc.0c01488

    • Peer Reviewed
  • [Journal Article] Electron Binding in a Superatom with a Repulsive Coulomb Barrier: The Case of [Ag44(SC6H3F2)30]4- in the Gas Phase2020

    • Author(s)
      Tasaka Yuriko、Nakamura Katsunosuke、Malola Sami、Hirata Keisuke、Kim Kuenhee、Koyasu Kiichirou、Hakkinen Hannu、Tsukuda Tatsuya
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 11 Pages: 3069~3074

    • DOI

      10.1021/acs.jpclett.0c00786

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Electron Microscopic Observation of an Icosahedral Au13 Core in Au25(SePh)18 and Reversible Isomerization between Icosahedral and Face-Centered Cubic Cores in Au144(SC2H4Ph)602020

    • Author(s)
      Takahata Ryo、Yamazoe Seiji、Maehara Yosuke、Yamazaki Kenji、Takano Shinjiro、Kurashige Wataru、Negishi Yuichi、Gohara Kazutoshi、Tsukuda Tatsuya
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Pages: 6907~6912

    • DOI

      10.1021/acs.jpcc.9b11412

    • Peer Reviewed
  • [Journal Article] CdTe quantum dots modified electrodes ITO-(Polycation/QDs) for carbon dioxide reduction to methanol2020

    • Author(s)
      Guzman Diego、Isaacs Mauricio、Tsukuda Tatsuya、Yamazoe Seiji、Takahata Ryo、Schrebler Ricardo、Burgos Ana、Osorio-Roman Igor、Castillo Francisco
    • Journal Title

      Applied Surface Science

      Volume: 509 Pages: 145386~145386

    • DOI

      10.1016/j.apsusc.2020.145386

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Acid-base equilibrium of the chromophore counterion results in distinct photoisomerization reactivity in the primary event of proteorhodopsin2019

    • Author(s)
      Chang Chun-Fu、Kuramochi Hikaru、Singh Manish、Abe-Yoshizumi Rei、Tsukuda Tatsuya、Kandori Hideki、Tahara Tahei
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 21 Pages: 25728~25734

    • DOI

      10.1039/C9CP04991F

    • Peer Reviewed
  • [Journal Article] Asymmetric aerobic oxidation of secondary alcohols catalyzed by poly(N-vinyl-2-pyrrolidone)-stabilized gold clusters modified with cyclodextrin derivatives2019

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

      Chemical Communications

      Volume: 55 Pages: 15033~15036

    • DOI

      10.1039/C9CC06770A

    • 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 Pages: 6892~6896

    • DOI

      10.1021/acs.jpclett.9b02920

    • Peer Reviewed
  • [Journal Article] Reductive Activation of Small Molecules by Anionic Coinage Metal Atoms and Clusters in the Gas Phase2019

    • Author(s)
      Muramatsu Satoru、Tsukuda Tatsuya
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 14 Pages: 3763~3772

    • DOI

      10.1002/asia.201901156

    • Peer Reviewed / Open Access
  • [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 Pages: 15994~16002

    • DOI

      10.1021/jacs.9b08055

    • Peer Reviewed
  • [Journal Article] Robust, Highly Luminescent Au13 Superatoms Protected by N-Heterocyclic Carbenes2019

    • Author(s)
      Narouz Mina R.、Takano Shinjiro、Lummis Paul A.、Levchenko Tetyana I.、Nazemi Ali、Kaappa Sami、Malola Sami、Yousefalizadeh Goonay、Calhoun Larry A.、Stamplecoskie Kevin G.、Hakkinen Hannu、Tsukuda Tatsuya、Crudden Cathleen M.
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Pages: 14997~15002

    • DOI

      10.1021/jacs.9b07854

    • Peer Reviewed / Int'l Joint Research
  • [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 Pages: 14048~14051

    • DOI

      10.1021/jacs.9b06254

    • Peer Reviewed
  • [Journal Article] Characterization of chemically modified gold and silver clusters in gas phase2019

    • Author(s)
      Hirata Keisuke、Tomihara Ryohei、Kim Kuenhee、Koyasu Kiichirou、Tsukuda Tatsuya
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 21 Pages: 17463~17474

    • DOI

      10.1039/C9CP02622C

    • Peer Reviewed / Open Access
  • [Journal Article] Elucidating the Doping Effect on the Electronic Structure of Thiolate‐Protected Silver Superatoms by Photoelectron Spectroscopy2019

    • Author(s)
      Kim Kuenhee、Hirata Keisuke、Nakamura Katsunosuke、Kitazawa Hirokazu、Hayashi Shun、Koyasu Kiichirou、Tsukuda Tatsuya
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Pages: 11637~11641

    • DOI

      10.1002/anie.201901750

    • Peer Reviewed
  • [Journal Article] Ultrathin Gold Nanowires and Nanorods2019

    • Author(s)
      Takahata Ryo、Tsukuda Tatsuya
    • Journal Title

      Chemistry Letters

      Volume: 48 Pages: 906~915

    • DOI

      10.1246/cl.190313

    • Peer Reviewed / Open Access
  • [Journal Article] Structural Evolution of Iridium Oxide Cluster Anions IrnOm- (n = 5-8) with Sequential Oxidation: Binding Mode of O Atoms and Ir Framework2019

    • Author(s)
      Tomihara Ryohei、Koyasu Kiichirou、Nagata Toshiaki、Wu Jenna W. J.、Nakano Motoyoshi、Ohshimo Keijiro、Misaizu Fuminori、Tsukuda Tatsuya
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 123 Pages: 15301~15306

    • DOI

      10.1021/acs.jpcc.9b02935

    • Peer Reviewed
  • [Journal Article] Reduction-resistant [Au25(cyclohexanethiolate)18]0 with an Icosahedral Au13 Core2019

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

      Chemistry Letters

      Volume: 48 Pages: 885~887

    • DOI

      10.1246/cl.190306

    • Peer Reviewed / Open Access
  • [Journal Article] Photoinduced Thermionic Emission from [M25(SR)18]- (M = Au, Ag) Revealed by Anion Photoelectron Spectroscopy2019

    • Author(s)
      Hirata Keisuke、Kim Kuenhee、Nakamura Katsunosuke、Kitazawa Hirokazu、Hayashi Shun、Koyasu Kiichirou、Tsukuda Tatsuya
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 123 Pages: 13174~13179

    • DOI

      10.1021/acs.jpcc.9b03455

    • Peer Reviewed
  • [Journal Article] Synthesis of Trimetallic (HPd@M2Au8)3+ Superatoms (M = Ag, Cu) via Hydride-Mediated Regioselective Doping to (Pd@Au8)2+2019

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

      ACS Omega

      Volume: 4 Pages: 7070~7075

    • DOI

      10.1021/acsomega.9b00575

    • Peer Reviewed / Open Access
  • [Journal Article] xTunes: A new XAS processing tool for detailed and on-the-fly analysis2019

    • Author(s)
      Asakura Hiroyuki、Yamazoe Seiji、Misumi Teppei、Fujita Aki、Tsukuda Tatsuya、Tanaka Tsunehiro
    • Journal Title

      Radiation Physics and Chemistry

      Volume: 未定 Pages: in press

    • Peer Reviewed
  • [Journal Article] クラスター間の自発的電子移動による開殻系クラスター[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,

      Volume: 18 Pages: 21~26

    • Peer Reviewed
  • [Journal Article] Structures of Chemically Modified Superatoms2019

    • Author(s)
      Tsukuda Tatsuya
    • Journal Title

      Molecular Science

      Volume: 13 Pages: A0108~A0108

    • DOI

      10.3175/molsci.13.A0108

    • Peer Reviewed / Open Access
  • [Presentation] Gas-phase studies on chemically-synthesized Au and Ag superatoms2020

    • Author(s)
      Tatsuya Tsukuda
    • Organizer
      Symposium on Size Selected Clusters
    • Int'l Joint Research / Invited
  • [Presentation] Electronic structures of ligand-protected Au/Ag superatoms2020

    • Author(s)
      Tatsuya Tsukuda
    • Organizer
      Gordon Research Conference; Towards Atomic Precision in Nanochemistry
    • Int'l Joint Research / Invited
  • [Presentation] 有機修飾金属超原子―最近の進展から2019

    • Author(s)
      佃達哉
    • Organizer
      Ambitious物質科学セミナー
    • Invited
  • [Presentation] 金属クラスターの化学2019

    • Author(s)
      佃達哉
    • Organizer
      第10回表面化学チュートリアル
    • Invited
  • [Presentation] Chemically modified gold and silver superatoms: From liquid phase to gas phase2019

    • Author(s)
      Tatsuya Tsukuda
    • Organizer
      The 76th Fujihara Seminar, International Workshop on Designer Nanocluster Materials: From Gas Phase to Condensed Phase
    • Int'l Joint Research / Invited
  • [Presentation] Characterization of ligand-protected gold and silver clusters in gas phase2019

    • Author(s)
      Tatsuya Tsukuda
    • Organizer
      International Symposium on Monolayer-Protected Clusters (ISMPC19)
    • Int'l Joint Research / Invited
  • [Presentation] Characterization of chemically modified gold and silver clusters in gas phase2019

    • Author(s)
      Tatsuya Tsukuda
    • Organizer
      2nd Asian Symposium on Nanoscience and Nanotechnology "Fundamentals and Applications of Nanoclusters and Nanoparticles"
    • Int'l Joint Research / Invited
  • [Presentation] Hydride-mediated transformations of gold-based superatoms2019

    • Author(s)
      Tatsuya Tsukuda
    • Organizer
      ChinaNANO2019
    • Int'l Joint Research / Invited
  • [Presentation] 化学修飾された超原子と超原子分子2019

    • Author(s)
      佃達哉
    • Organizer
      東北大学理学部化学教室一般雑誌会講演会
    • Int'l Joint Research / Invited
  • [Presentation] Chemically modified gold and silver superatoms: recent topics2019

    • Author(s)
      Tatsuya Tsukuda
    • Organizer
      Seminar at Shanxi Normal University
    • Int'l Joint Research / Invited
  • [Presentation] Chemically modified gold and silver superatoms: recent topics2019

    • Author(s)
      Tatsuya Tsukuda
    • Organizer
      Seminar at Tsinghua University
    • Int'l Joint Research / Invited
  • [Presentation] ナノの世界の美しさー超原子とその周期表―2019

    • Author(s)
      佃達哉
    • Organizer
      第4回駒場サイエンス倶楽部
    • Invited
  • [Book] Physical Chemistry of Cold Gas-Phase Functional Molecules and Clusters2019

    • Author(s)
      Takayuki Ebata, Masaaki Fujii
    • Total Pages
      395
    • Publisher
      Verlag: Springer Singapore
    • ISBN
      978-981-13-9370-9
  • [Remarks] 東京大学理学系理学系研究科化学専攻化学反応研究室

    • URL

      http://www.chem.s.u-tokyo.ac.jp/users/chemreact/index.html

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Published: 2021-01-27  

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