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Published on: January 17, 2017
The electrooxidation-induced structural changes of gold di-superatomic molecules: Au23vs. Au25
Shota Matsuo1, Seiji Yamazoe2, Jing-Qiang Goh3
1Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan. tsukuda@chem.s.u-tokyo.ac.jp.
Abstract:
The gold cluster compounds Au38(SC2H4Ph)24 and [Au25(PPh3)10(SC2H4Ph)5Cl2](2+) are known to possess bi-icosahedral Au23 and Au25 cores, respectively, inside their ligand shells. These Au cores can be viewed as quasi-molecules composed of two Au13 superatoms sharing three and one Au(+) atoms, respectively. In the present work, we studied the structural changes of these gold di-superatomic molecules upon electrooxidation via spectroelectrochemical techniques, X-ray absorption fine structure analysis, and density functional theory calculations. The Au23 core was electrochemically stable, but the Au25 core underwent irreversible structural change. This marked difference in the stability of the oxidized states is ascribed to differences in the bonding scheme of Au13 units and/or the bonding nature of the protecting ligands.
