title: The electrooxidation-induced structural changes of gold di-superatomic molecules: Au23vs. Au25.
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.
authors.affiliation: Department 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.
authors.forename: Shota
authors.initials: S
authors.lastname: Matsuo
authors.affiliation: Department 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 and Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520, Japan.
authors.forename: Seiji
authors.initials: S
authors.lastname: Yamazoe
authors.affiliation: Department of Physics, Tampere University of Technology, P.O. Box 692, FI-33101 Tampere, Finland and COMP Centre of Excellence, Department of Applied Physics, Aalto University, FI-00076 Aalto, Finland.
authors.forename: Jing-Qiang
authors.initials: JQ
authors.lastname: Goh
authors.affiliation: Department of Physics, Tampere University of Technology, P.O. Box 692, FI-33101 Tampere, Finland and COMP Centre of Excellence, Department of Applied Physics, Aalto University, FI-00076 Aalto, Finland.
authors.forename: Jaakko
authors.initials: J
authors.lastname: Akola
authors.affiliation: Department 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 and Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520, Japan.
authors.forename: Tatsuya
authors.initials: T
authors.lastname: Tsukuda