Rational Design of Highly Phosphorescent Nanoclusters for Efficient Photocatalytic Oxidation.

Analyzing the molecular structure-photophysical property correlations of metal nanoclusters to accomplish function-oriented photocatalysis could be challenging. Here, the selective heteroatom alloying has been exploited to a nanocluster, making up a structure-correlated nanocluster series, including homogold , bimetallic and , trimetallic , and tetrametallic . Their structure-dependent photophysical properties were investigated due to the atomically precise structures of these nanoclusters. Cu-alloyed showed intense phosphorescence and the highest singlet oxygen production efficiency. Moreover, the generation of O species from excited nanoclusters enabled as a suitable catalyst for efficient photocatalytic oxidation of silyl enol ethers to produce α,β-unsaturated carbonyl compounds. The generality and applicability of the catalysts toward different photocatalytic oxidations were assessed. Overall, this study presents an intriguing -based cluster series enabling an atomic-level understanding of structure-photophysical property correlations, which hopefully provides guidance for the fabrication of cluster-based catalysts with customized photocatalytic performance.