title: Effect of Copper Doping on Electronic Structure, Geometric Structure, and Stability of Thiolate-Protected Au25 Nanoclusters.
abstract: Several recent studies have attempted to impart [Au25(SR)18](-) with new properties by doping with foreign atoms. In this study, we studied the effect of copper doping on the electronic structure, geometric structure, and stability of [Au25(SR)18](-) with the aim of investigating the effect of foreign atom doping of [Au25(SR)18](-). CunAu25-n(SC2H4Ph)18 was synthesized by reducing complexes formed by the reaction between metal salts (copper and gold salts) and PhC2H4SH with NaBH4. Mass analysis revealed that the products contained CunAu25-n(SC2H4Ph)18 (n = 1-5) in high purity. Experimental and theoretical analysis of the synthesized clusters revealed that copper doping alters the optical properties and redox potentials of the cluster, greatly distorts its geometric structure, and reduces the cluster stability in solution. These findings are expected to be useful for developing design guidelines for functionalizing [Au25(SR)18](-) through doping with foreign atoms.
authors: †Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.|‡Research Institute for Science and Technology, Energy and Environment Photocatalyst Research Division, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
authors: Yuichi
authors: Y
authors: Negishi
authors: †Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
authors: Kenta
authors: K
authors: Munakata
authors: †Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
authors: Wataru
authors: W
authors: Ohgake
authors: §Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Myodaiji, Okazaki, Aichi 444-8585, Japan.
authors: Katsuyuki
authors: K
authors: Nobusada
keywords: electronic structure; foreign atom doping; geometric structure; stability; synthesis; thiolate-protected gold cluster