Hexane-Driven Icosahedral to Cuboctahedral Structure Transformation of Gold Nanoclusters

• DOI: 10.1021/ja306923a
• Publication Date: 2012-10-10T21:20:26Z
• Authors: Yuanyuan Li; Hao Cheng; Tao Yao; Zhihu Sun; Wensheng Yan; Yong Jiang; Yi Xie; Yongfu Sun; Yuanyuan Huang; Shoujie Liu; Jing Zhang; Yaning Xie; Tiandou Hu; Lina Yang; Ziyu Wu; Shiqiang Wei
• Keywords: Time Factors; Molecular Structure; 9. Industry and infrastructure; Hexanes; Metal Nanoparticles; Gold; 02 engineering and technology; 0210 nano-technology

Whether and how nanoclusters possessing a rich diversity of possible geometric configurations can transform from one structural type to another are critical issues in cluster science. Here we demonstrate an icosahedral-to-cuboctahedral structural transformation of Au nanoclusters driven by changing the chemical environment. For icosahedral Au(13) clusters protected by a mixture of dodecanethiol and triphenylphosphine ligands, solvent exchange of ethanol by hexane leads to quick selective desorption of the thiolate layers from the cluster surface. The surviving Au cores then undergo a much slower energy-minimization process via structural rearrangement, stabilized in the cuboctahedral structure and protected by triphenylphosphine in the hexane environment. In response to the dramatically changed atomic structure, the character of the electronic structure of the Au clusters is converted from semiconducting to metallic. This work addresses the structure-property correlation and its strong dependence on the chemical environment for metal nanoclusters.