The electrooxidation-induced structural changes of gold di-superatomic molecules: Au-23 vs. Au-25

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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en

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6

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Physical Chemistry Chemical Physics, Volume 18, issue 6, pp. 4822-4827

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The gold cluster compounds Au-38(SC2H4Ph)(24) and [Au-25(PPh3)(10)(SC2H4Ph)(5)Cl-2](2+) are known to possess bi-icosahedral Au-23 and Au-25 cores, respectively, inside their ligand shells. These Au cores can be viewed as quasi-molecules composed of two Au-13 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 Au-23 core was electrochemically stable, but the Au-25 core underwent irreversible structural change. This marked difference in the stability of the oxidized states is ascribed to differences in the bonding scheme of Au-13 units and/or the bonding nature of the protecting ligands.

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Matsuo, S, Yamazoe, S, Goh, J-Q, Akola, J & Tsukuda, T 2016, 'The electrooxidation-induced structural changes of gold di-superatomic molecules : Au-23 vs. Au-25', Physical Chemistry Chemical Physics, vol. 18, no. 6, pp. 4822-4827. https://doi.org/10.1039/c5cp06969f