Photosynergetic ligand-exchange for modular synthesis of copper nanoclusters

The abundance, low cost, and distinctive properties of copper are driving increased interest in copper nanoclusters. However, modular synthesis of such clusters remains underdeveloped. Here, we report a modular strategy for constructing copper nanoclusters via the synergistic combination of photochemical activation and nanoscale ligand-exchange. Using a readily scalable precursor—[Cu14(TXP35)4(BnSe)12H]+ (Cu14)—we demonstrate its photo-facilitated ligand-exchange with exogenous phosphine ligands, enabling the precise synthesis of 18 copper nanoclusters. This approach also allows functional motifs, such as chiral ligands, to be incorporated into the cluster framework. Mechanistic studies supported by in situ characterization reveal that upon light exposure, Cu14 decomposes into diverse intermediates—including copper atoms/clusters, selenium, benzyl groups, TXP35, and their combinations—which then reassemble in the presence of external ligands to form new nanoclusters. Our modular nanosynthesis establishes a versatile platform for the atomic-level engineering of copper nanoclusters and is expected to advance the tailored design of cluster-based nanomaterials. While interest in copper nanoclusters has grown due to the high abundance, low cost, and unique properties of copper, modular synthesis remains underdeveloped. Here, the authors report a strategy for constructing structurally well-defined copper nanoclusters through the synergistic combination of photochemical activation and nanoscale ligand-exchange.