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

Shota Matsuo, Seiji Yamazoe, Jing-Qiang Goh, Jaakko Akola, Tatsuya Tsukuda*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

8 Citations (Scopus)
48 Downloads (Pure)

Abstract

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.

Original languageEnglish
Pages (from-to)4822-4827
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number6
DOIs
Publication statusPublished - 14 Feb 2016
MoE publication typeA1 Journal article-refereed

Keywords

  • OPTICAL-PROPERTIES
  • CRYSTAL-STRUCTURE
  • BUILDING-BLOCKS
  • PROTECTED AU-25
  • CLUSTERS
  • NANOCLUSTER
  • STABILITY

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