Fluorescent Gold Nanoclusters with Interlocked Staples and a Fully Thiolate-Bound Kernel

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• 作者：Zibao Gan ; Yuejian Lin ; Lun Luo ; Guangmei Han ; Wei Liu ; Zhengjie Liu ; Chuanhao Yao ; Linhong Weng ; Lingwen Liao ; Jishi Chen ; Xu Liu ; Yi Luo ; Chengming Wang ; Shiqiang Wei and Prof. Zhikun Wu
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：September 12, 2016
• 年：2016
• 卷：128
• 期：38
• 页码：11739-11743
• 全文大小：2846K
• ISSN：1521-3757

文摘

The structural features that render gold nanoclusters intrinsically fluorescent are currently not well understood. To address this issue, highly fluorescent gold nanoclusters have to be synthesized, and their structures must be determined. We herein report the synthesis of three fluorescent Au₂₄(SR)₂₀ nanoclusters (R=C₂H₄Ph, CH₂Ph, or CH₂C₆H₄^tBu). According to UV/Vis/NIR, differential pulse voltammetry (DPV), and X-ray absorption fine structure (XAFS) analysis, these three nanoclusters adopt similar structures that feature a bi-tetrahedral Au₈ kernel protected by four tetrameric Au₄(SR)₅ motifs. At least two structural features are responsible for the unusual fluorescence of the Au₂₄(SR)₂₀ nanoclusters: Two pairs of interlocked Au₄(SR)₅ staples reduce the vibration loss, and the interactions between the kernel and the thiolate motifs enhance electron transfer from the ligand to the kernel moiety through the Au−S bonds, thereby enhancing the fluorescence. This work provides some clarification of the structure–fluorescence relationship of such clusters.