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 Au 15 nanocluster, making up a structure-correlated nanocluster series, including homogold Au 15 , bimetallic Ag x Au 15- x and Cu x Au 15- x , trimetallic Ag x Cu y Au 15- x - y , and tetrametallic Pt 1 Ag x Cu y Au 15- x - y . Their structure-dependent photophysical properties were investigated due to the atomically precise structures of these nanoclusters. Cu-alloyed Cu x Au 15- x showed intense phosphorescence and the highest singlet oxygen production efficiency. Moreover, the generation of 1 O 2 species from excited nanoclusters enabled Cu x Au 15- x 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 Cu x Au 15- x catalysts toward different photocatalytic oxidations were assessed. Overall, this study presents an intriguing Au 15 -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.