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Fluorescent Gold Nanoclusters with Interlocked Staples and a Fully Thiolate‐Bound Kernel
Authors: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  Prof. Zhikun Wu
Affiliation:1. Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanostructures, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, China;2. Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai, China;3. State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, China;4. Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, China;5. National Synchrotron Radiation Facility, University of Science and Technology of China, Hefei, China;6. Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China
Abstract: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 CH2C6H4tBu). 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.
Keywords:fluorescence  gold  nanoclusters  synthetic methods
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