Giant Emission Enhancement of Solid‐State Gold Nanoclusters by Surface Engineering
Chuanhao Yao, Cong‐Qiao Xu, In‐Hyeok Park, Meng Zhao, Ziyu Zhu, Jing Li, Jing Li, Xiao Hai, Hanyan Fang, Yong Zhang, Gennevieve Macam, Jinghua Teng, Lin Li, Qing‐Hua Xu, Feng‐Chuan Chuang, Junpeng Lü, Junpeng Lü, Chenliang Su, Jun Li, Jun Li, Jiong Lu, Jiong Lu
Abstract
Abstract Ligand‐induced surface restructuring with heteroatomic doping is used to precisely modify the surface of a prototypical [Au 25 (SR 1 ) 18 ] − cluster ( 1 ) while maintaining its icosahedral Au 13 core for the synthesis of a new bimetallic [Au 19 Cd 3 (SR 2 ) 18 ] − cluster ( 2 ). Single‐crystal X‐ray diffraction studies reveal that six bidentate Au 2 (SR 1 ) 3 motifs (L2) attached to the Au 13 core of 1 were replaced by three quadridentate Au 2 Cd(SR 2 ) 6 motifs (L4) to create a bimetallic cluster 2 . Experimental and theoretical results demonstrate a stronger electronic interaction between the surface motifs (Au 2 Cd(SR 2 ) 6 ) and the Au 13 core, attributed to a more compact cluster structure and a larger energy gap of 2 compared to that of 1 . These factors dramatically enhance the photoluminescence quantum efficiency and lifetime of crystal of the cluster 2 . This work provides a new route for the design of a wide range of bimetallic/alloy metal nanoclusters with superior optoelectronic properties and functionality.