Abstract
AbstractLigand‐induced surface restructuring with heteroatomic doping is used to precisely modify the surface of a prototypical [Au25(SR1)18]− cluster (1) while maintaining its icosahedral Au13 core for the synthesis of a new bimetallic [Au19Cd3(SR2)18]− cluster (2). Single‐crystal X‐ray diffraction studies reveal that six bidentate Au2(SR1)3 motifs (L2) attached to the Au13 core of 1 were replaced by three quadridentate Au2Cd(SR2)6 motifs (L4) to create a bimetallic cluster 2. Experimental and theoretical results demonstrate a stronger electronic interaction between the surface motifs (Au2Cd(SR2)6) and the Au13 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.
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