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

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; Zhikun Wu

doi:10.1002/anie.201606661

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

Angew Chem Int Ed Engl. 2016 Sep 12;55(38):11567-71. doi: 10.1002/anie.201606661. Epub 2016 Aug 16.

Authors

Zibao Gan¹, Yuejian Lin², Lun Luo³, Guangmei Han⁴, Wei Liu⁵, Zhengjie Liu⁴, Chuanhao Yao¹, Linhong Weng², Lingwen Liao¹, Jishi Chen¹, Xu Liu¹, Yi Luo³, Chengming Wang⁶, Shiqiang Wei⁵, Zhikun Wu⁷

Affiliations

¹ Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanostructures, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, 230031, China.
² Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai, 200433, China.
³ State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, 116024, China.
⁴ Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei, 230031, China.
⁵ National Synchrotron Radiation Facility, University of Science and Technology of China, Hefei, 230029, China.
⁶ Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China.
⁷ Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanostructures, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, 230031, China. zkwu@issp.ac.cn.

PMID: 27529838
DOI: 10.1002/anie.201606661

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=C2 H4 Ph, CH2 Ph, or CH2 C6 H4 (t) Bu). 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.

Publication types

Research Support, Non-U.S. Gov't