2004 Fiscal Year Final Research Report Summary
Interfacial Control and Dynamic Assembly of Organic Molecule-functionalized Metal Nanoclusters
| Project/Area Number |
15550044
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Kinki University |
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Principal Investigator |
FUJIHARA Hisashi Kinki University, Applied Chemistry, Professor, 理工学部, 教授 (30190101)
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| Project Period (FY) |
2003 – 2004
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| Keywords | Metal Nanoclusters / Interfacial Control / Self-Assembly / Ionic Liquid / Asymmetric Reaction / Metal Complex |
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| 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.
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