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Updated: Mar 27, 2026
Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Hierarchy of bond stiffnesses within icosahedral-based gold clusters protected by thiolates
Seiji Yamazoe1,2, Shinjiro Takano1, Wataru Kurashige3
1Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
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.
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