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2004 Fiscal Year Final Research Report Summary

Interfacial Control and Dynamic Assembly of Organic Molecule-functionalized Metal Nanoclusters

Research Project

Project/Area Number 15550044
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKinki University

Principal Investigator

FUJIHARA Hisashi  Kinki University, Applied Chemistry, Professor, 理工学部, 教授 (30190101)

Project Period (FY) 2003 – 2004
KeywordsMetal Nanoclusters / Interfacial Control / Self-Assembly / Ionic Liquid / Asymmetric Reaction / Metal Complex
Research Abstract

The project involves the following topics. (1)Novel chiral 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [BINAP]-Pd nanoclusters (1.9 nm) are efficient nano-catalyst for the asymmetric hydrosilylation of olefin under mild conditions. We have found a significant difference in the catalytic activity between BINAP-Pd nanoclusters and Pd-BINAP complex. This finding indicates a new aspect in the field of asymmetric reaction catalyzed by chiral phosphine-stabilized metal nanoclusters and transition metal-phosphine complexes. (2)We have successfully prepared a series of novel gold nanoclusters (zwitter-Au) modified with zwitterionic liquid consisting of an imidazolium cation and a sulfonate anion. Zwitter-Au has great stability in aqueous solutions with high concentrations of electrolytes, ionic liquids, and protein. These first examples of zwitter-Au open up interesting perspectives in the fields of reaction and catalysis using water- and ionic liquid-soluble metal nanoclusters based on green chemistry, and electronic and bio-analytical applications. (3)The reduction of tetrachloroaurate with sodium borohydride in the presence of 2,2':6',2"-terpyridyloctanethiol gave the terpyridine-functionalized gold nanoclusters (Tpy-Au, core size 2.0 nm). Metal complexation of Tpy-Au with ruthenium-terpyridyl trichloride, Ru(tpy)Cl_3, led to the new gold nanoclusters bearing ruthenium-terpyridine complex (Ru-Tpy-Au, core size 5.5 nm) which showed a characteristic MLCT (metal-to-ligand charge transfer) band in the visible region at 483 nm due to the terpyridine-ruthenium complex and a plasmon resonance at 〜510 nm in the UV-vis spectrum. The redox behavior of Ru-Tpy-Au was studied by cyclic voltammetry. Surface modification of metal electrode was performed by the electropolymerization of the pyrrole-functionalized Ru-Tpy-Au nanoclusters (Pyr-Ru-Tpy-Au) which were obtained from the ligand-exchange reaction of Ru-Tpy-Au with ω-(N-pyrrolyl)decanethiol.

  • Research Products

    (8 results)

All 2005 2004 2003

All Journal Article (8 results)

  • [Journal Article] Remarkably Stable Gold Nanoparticles Functionalized with a Zwitterionic Liquid Based on Imidazolium-sulfonate in a High Concentration of Aqueous Electrolyte and Ionic Liquid2005

    • Author(s)
      R.Tatumi, H.Fujihara
    • Journal Title

      Chem.Commun.

      Pages: 83-85

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation and Characterization of Gold Nanoparticles with Ruthenium-terpyridyl Complex, and Electropolymerization of Their Pyrrole-modified Metal Nanocomposites2005

    • Author(s)
      M.Ito, T.Tsukatani, H.Fujihara
    • Journal Title

      J.Mater.Chem.

      Pages: 960-964

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Electrochemical properties of self-assembled monolayers with tetracyanoanthra-quinodimethane-disulfide as a new electron acceptor on gold electrode2005

    • Author(s)
      Y.Satake, H.Fujihara
    • Journal Title

      Electrochemistry 73

      Pages: 38-40

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis and Electropolymerization of Terthiophene-modified Gold and Palladium Nanoparticles : Metal Nanoparticle-Polythiophene Composites2005

    • Author(s)
      Y.Satake, S.Ito, H.Fujihara
    • Journal Title

      J.Jpn.Soc.Colour Mater. (in press)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Metal Ion-Mediated Assembly of Redox-active Oligoethyleneoxy-functionalized Gold Nanoparticles and Their Immobilization on a Metal Electrode2005

    • Author(s)
      Y.Satake, S.Wakatsuki, M.Watanabe, S.Ito, H.Fujihara
    • Journal Title

      J.Jpn.Soc.Colour Mater. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Electrochemical Properties of Redox-active Tetrathiafulvalene and Fullerene C60-functionalized Gold Nanoparticles, and Their Nanocomposite Films-modified Electrodes2005

    • Author(s)
      Y.Satake, H.Nakai, S.Ito, H.Fujihara
    • Journal Title

      J.Jpn.Soc.Colour Mater. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Self-assembled Spherical Aggregates of Gold Nanoparticles and Their Network Ensembles Mediated by Metal Ion Recognition2004

    • Author(s)
      T.Goto, H.Fujihara
    • Journal Title

      J.Mater.Sci. 39

      Pages: 2171-2173

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Chiral Bisphosphine BINAP-Stabilized Gold and Palladium Nanoparticles with Small Size and Their Palladium Nanoparticle-Catalyzed Asymmetric Reaction2003

    • Author(s)
      M.Tamura, H.Fujihara
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 15742-15743

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

URL: 

Published: 2006-07-11  

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