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

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

doi:10.1039/c5cp06969f

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

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

Research output: Contribution to journal › Article › Scientific › peer-review

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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.

Original language	English
Pages (from-to)	4822-4827
Number of pages	6
Journal	Physical Chemistry Chemical Physics
Volume	18
Issue number	6
DOIs	https://doi.org/10.1039/c5cp06969f
Publication status	Published - 2016
Publication type	A1 Journal article-refereed

Publication forum classification

Publication forum level 1

ASJC Scopus subject areas

Physical and Theoretical Chemistry
General Physics and Astronomy

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10.1039/c5cp06969fLicence: CC BY

Matsuo et al. 2016
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Final published version, 2.23 MBLicence: CC BY

http://urn.fi/URN:NBN:fi:tty-201702101112

Cite this

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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.",

author = "Shota Matsuo and Seiji Yamazoe and Jing-Qiang Goh and Jaakko Akola and Tatsuya Tsukuda",

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T1 - The electrooxidation-induced structural changes of gold di-superatomic molecules

T2 - Au23vs. Au25

AU - Matsuo, Shota

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AU - Goh, Jing-Qiang

AU - Akola, Jaakko

AU - Tsukuda, Tatsuya

PY - 2016

Y1 - 2016

N2 - 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.

AB - 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.

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DO - 10.1039/c5cp06969f

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