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The electrooxidation-induced structural changes of gold di-superatomic molecules: Au23vs. Au25

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Details

Original languageEnglish
Pages (from-to)4822-4827
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number6
DOIs
Publication statusPublished - 2016
Publication typeA1 Journal article-refereed

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.

Publication forum classification

Field of science, Statistics Finland