Frustrated Lewis Pair and Photocatalysis Synergistically Promote Copper Nanocluster Catalysis

We present a type of synergistic catalyst that integrates Frustrated Lewis Pair (FLP) and photocatalytic (PC) functionalities on an atomically precise copper nanocluster. By strategically functionalizing the cluster surface with 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol (TRZ), we successfully synthesize a structurally well-defined nanocluster [Cu₂₀(TRZ)₉(4-F₃PPh₃)₂H₄]^2-. The TRZ ligands serve a triple function: they not only stabilize the nanocluster framework but also furnish nitrogen-based Lewis basic sites. These sites, in conjunction with surface-exposed copper atoms acting as Lewis acids, form FLP-active centers capable of activating small molecules such as silanes under mild conditions. Furthermore, the TRZ ligand's triazine moiety acts as an efficient photoredox unit, driving the photocatalytic production of hydrogen peroxide through oxygen reduction. This activity, when integrated with the FLP functionality, results in an integrated system that exhibits high efficiency and selectivity in the catalytic oxidation of silanes to silanols. The catalyst demonstrates outstanding activity, selectivity, and stability under ambient conditions. This study not only presents a generalizable strategy for embedding FLP-PC bifunctionality in metal nanoclusters but also confirms the feasibility of designing high-performance cluster catalysts that operate via synergistic mechanistic pathways. The integration of FLP and PC functionalities supports efficient and selective transformations relevant to sustainable catalysis.