Hierarchy of bond stiffnesses within icosahedral-based gold clusters protected by thiolates

Seiji Yamazoe, Shinjiro Takano, Wataru Kurashige, Toshihiko Yokoyama, Kiyofumi Nitta, Yuichi Negishi and Tatsuya Tsukuda ()
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Seiji Yamazoe: School of Science, The University of Tokyo
Shinjiro Takano: School of Science, The University of Tokyo
Wataru Kurashige: Faculty of Science, Tokyo University of Science
Toshihiko Yokoyama: Institute for Molecular Science, Myodaiji
Kiyofumi Nitta: Japan Synchrotron Radiation Research Institute
Yuichi Negishi: Faculty of Science, Tokyo University of Science
Tatsuya Tsukuda: School of Science, The University of Tokyo

Nature Communications, 2016, vol. 7, issue 1, 1-7

Abstract: Abstract Unique thermal properties of metal clusters are believed to originate from the hierarchy of the bonding. However, an atomic-level understanding of how the bond stiffnesses are affected by the atomic packing of a metal cluster and the interfacial structure with the surrounding environment has not been attained to date. Here we elucidate the hierarchy in the bond stiffness in thiolate-protected, icosahedral-based gold clusters Au25(SC2H4Ph)18, Au38(SC2H4Ph)24 and Au144(SC2H4Ph)60 by analysing Au L3-edge extended X-ray absorption fine structure data. The Au–Au bonds have different stiffnesses depending on their lengths. The long Au–Au bonds, which are more flexible than those in the bulk metal, are located at the icosahedral-based gold core surface. The short Au–Au bonds, which are stiffer than those in the bulk metal, are mainly distributed along the radial direction and form a cyclic structural backbone with the rigid Au–SR oligomers.

Date: 2016
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DOI: 10.1038/ncomms10414

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