Total Structure Determination of Au21(S-Adm)15 and Geometrical/Electronic Structure Evolution of Thiolated Gold Nanoclusters

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• 作者：Shuang Chen ; Lin Xiong ; Shuxin Wang ; Zhongyun Ma ; Shan Jin ; Hongting Sheng ; Yong Pei ; Manzhou Zhu
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：August 31, 2016
• 年：2016
• 卷：138
• 期：34
• 页码：10754-10757
• 全文大小：401K
• 年卷期：0
• ISSN：1520-5126

文摘

The larger size gold nanoparticles typically adopt a face-centered cubic (fcc) atomic packing, while in the ultrasmall nanoclusters the packing styles of Au atoms are diverse, including fcc, hexagonal close packing (hcp), and body-centered cubic (bcc), depending on the ligand protection. The possible conversion between these packing structures is largely unknown. Herein, we report the growth of a new Au₂₁(S-Adm)₁₅ nanocluster (S-Adm = adamantanethiolate) from Au₁₈(SR)₁₄ (SR = cyclohexylthiol), with the total structure determined by X-ray crystallography. It is discovered that the hcp Au₉-core in Au₁₈(SR)₁₄ is transformed to a fcc Au₁₀-core in Au₂₁(S-Adm)₁₅. Combining with density functional theory (DFT) calculations, we provide critical information about the growth mechanism (geometrical and electronic structure) and the origin of fcc-structure formation for the thiolate-protected gold nanoclusters.