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2005 Fiscal Year Final Research Report Summary

Electronic Structures and Photoluminescence of Monolayer-Protected Metal Clusters

Research Project

Project/Area Number 16510079
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Nanostructural science
Research InstitutionInstitute for Molecular Science

Principal Investigator

TSUKUDA Tatsuya  Institute for Molecular Science, Research Center for Molecular Scale Nanoscience, Associate Professor, 分子スケールナノサイエンスセンター, 助教授 (90262104)

Co-Investigator(Kenkyū-buntansha) NEGISHI Yuichi  Institute for Molecular Science, Research Center for Molecular-Scale Nanoscience, Research Associate, 分子スケールナノサイエンスセンター, 助手 (20332182)
NAGATA Takashi  The University of Tokyo,Graduate School of Arts and Sciences, Department of Basic Sciences, Professor, 大学院・総合文化研究科, 教授 (10164211)
NOBUSADA Katsuyuki  Institute for Molecular Science, Department of Theoretical Studies, Assistant Professor, 理論分子科学研究系, 助教授 (50290896)
Project Period (FY) 2004 – 2005
Keywordsgold cluster / thiol / PAGE / mass analysis / photoluminescence / GPC
Research Abstract

We have developed a synthetic method of thiolate-protected gold clusters with well-defined chemical compositions. The method is based on size separation by using polyacrylamide gel electrophoresis (PAGE) and gel permeation chromatography (GPC) and mass spectrometric characterization. Electronic and geometrical structures of the thiolated gold (Au : SR) clusters thus synthesized were studied by using various spectroscopic methods and theoretical calculations. The findings are summarized as follows.
1)The Au : SR clusters formed by reduction of the corresponding Au(I)-SR polymer correspond to trapped intermediates of the growing clusters. We observed several magic-numbered gold clusters such as Au25(SG)18 and Au55(SC18)32, where GSH and C18SH represent glutathione and octadecanethiol, respectively.
2)The small Au : SR clusters exhibit photoluminescence with quantum yield of 10^<-3>- 10^<-4>, which is significantly larger than that of bulk gold (10^<-10>). This enhancement is attributable to the quasi-molecular electronic structures. The emission wavelengths are nearly constant irrespective of the core size. This suggests that the PL originates from the Au-SR ring structures attached on the gold cluster surface. This structure model is supported by theoretical studies.

  • Research Products

    (20 results)

All 2006 2005 2004 Other

All Journal Article (20 results)

  • [Journal Article] Chromatographic isolation of "mssiing"Au_55 clusters protected by alkanethiolates2006

    • Author(s)
      H.Tsunoyama, Y.Negishi, T.Ysukuda
    • Journal Title

      Journal of the American Chemical Society 128

      Pages: 6036-6037

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Spectroscopic investigation of dendrimer-encapsulated gold nanoclusters2006

    • Author(s)
      M.Imamura, T.Miyashita, A.Tanaka, H.Yasuda, Y.Yanagimoto, Y.Negishi, T.Tsukuda
    • Journal Title

      Transaction of Material Research Society-Japan (印刷中)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] チオール保護金クラスターの精密合成 : サイズ特異的な構造・物性の解明に向けて2006

    • Author(s)
      佃達哉, 角山寛規, 柳本泰, 根岸雄一
    • Journal Title

      ナノ学会会報 4

      Pages: 53-58

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] 有機保護金ナノクラスターの精密合成-サイズ特異的な構造・触媒機能の解明に向けて2006

    • Author(s)
      佃達哉
    • Journal Title

      Electrochemistry 電気化学および工業物理化学 74

      Pages: 346-35O

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Chiroptical activity of BINAP-stabilized undecagold clusters2006

    • Author(s)
      Y.Yanagimoto, Y.Negishi, H.Fujihara, T.Tsukuda
    • Journal Title

      Journal of Physical Chemistry B 110

      Pages: 11611-11614

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Kinetic stabilization of growing gold clusters by passivation with thiolates2006

    • Author(s)
      Y.Negishi, Y.Takasugi, S.Sato, H.Yao, K.Kimura, T.Tsukuda
    • Journal Title

      Journal of Physical Chemistry B (印刷中)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Chromatographic isolation of "missing" Au_<55> clusters protected by alkanethiolates2006

    • Author(s)
      H.Tsunoyama, Y.Negishi, T.Tsukuda
    • Journal Title

      J.Am.Chem.Soc. 128

      Pages: 6036-6037

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Chiroptical activity of BINAP-stabilized undecagold clusters2006

    • Author(s)
      Y.Yanagimoto, Y.Negishi, H.Fujihara, T.Tsukuda
    • Journal Title

      J.Phys.Chem.B 110

      Pages: 11611-11614

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Precision syntheisi of thiolated gold clusters : Towards understanding the size-specific structures and properties2006

    • Author(s)
      T.Tsukuda, H.Tsunoyama, Y.Yanagimoto, Y.Negishi
    • Journal Title

      The Bulletin of the Society of Nano Science and Technology 4

      Pages: 53-58

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Size-specific properties and functions of gold clusters protected by organic molecules2006

    • Author(s)
      T.Tsukuda
    • Journal Title

      Electrochemistry 74

      Pages: 346-350

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Glutathione-protected gold clusters revisited : bridging the gap between gold(1)-thlolate complexes and thiolate-protected gold nanocrystals2005

    • Author(s)
      Y.Negishi, K.Nobusada, T.Tsukuda
    • Journal Title

      Journal of the American Chemical Society 127

      Pages: 5261-5270

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Large-scale synthesis of thiolated Au_25 Clusters via ligand exchange reactions phosophine-stabilized Au_11 clusters2005

    • Author(s)
      Y.Shichibu, Y.Negishi, T.Tukuda, T.Teranishi
    • Journal Title

      Journal of the American Chemical Society 127

      Pages: 13464-13465

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Subnanometer-sized gold clusters with dual molecular receptors synthesis and assembly one-dimensional arrangements2005

    • Author(s)
      Y.Negishi, H.Tsunoyama, Y.Yanagimoto, T.Tsukuda
    • Journal Title

      Chemistry Letters 34

      Pages: 1638-1639

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Glutathione-protected gold clusters revisited : bridging the gap between gold(I)-thiolate complexes and thiolate-protected gold nanocrystals2005

    • Author(s)
      Y.Negishi, K.Nobusada, T.Tsukuda
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 5261-5270

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Large-scale synthesis of thiolated Au_<25> clusters via ligand exchange reactions of phosphine-stabilized Au_<11> clusters2005

    • Author(s)
      Y.Shichibu, Y.Negishi, T.Tsukuda, T.Teranishi
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 13464-13465

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Subnanometer-sized gold clusters with dual molecular receptors : synthesis and assembly in one-dimensional arrangements2005

    • Author(s)
      Y.Negishi, H.Tsunoyama, Y.Yanagimoto, T.Tsukuda
    • Journal Title

      Chem.Lett. 34

      Pages: 1638-1639

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Magic-numbered Au_n clusters protected by glutathione monolayers (n=18,21,25,28,32,39) : isolation and spectroscopic characterization2004

    • Author(s)
      Y.Negishi, Y.Takasugi, S.Sato, H.Yao, K.Kimura, T.Tsukuda
    • Journal Title

      Journal of the American Chemical Society 126

      Pages: 6518-6519

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Magic-numbered Au_n clusters protected by glutathione monolayers (n=18, 21, 25, 28, 32, 39) : isolation and spectroscopic characterization2004

    • Author(s)
      Y.Negishi, Y.Takasugi, S.Sato, H.Yao, K.Kimura, T.Tsukuda
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 6518-6519

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Spectroscopic investigation of dendrimer-encapsulated gold nanoclusters

    • Author(s)
      M.Imamura, T.Miyashita, A.Tanaka, H.Yasuda, Y.Yanagimoto, Y.Negishi, T.Tsukuda
    • Journal Title

      Trans.MRS-J. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Kinetic stabilization of growing gold clusters by passivation with thiolates

    • Author(s)
      Y.Negishi, Y.Takasugi, S.Sato, H.Yao, K.Kimura, T.Tsukuda
    • Journal Title

      J.Phys.Chem.B (in press)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2007-12-13  

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