Structural Isomerism of {Ag} Nanocluster Encapsulated by Bowl-like Polyoxometalates.

The structural isomerism of atomically precise nanoclusters provides a preeminent theoretical model to investigate the structure-property relationships. Herein, we synthesized three bowl-like polyoxometalate (POM)-encapsulated Ag nanoclusters (denoted as {Ag(SbW)}-1, {Ag(SbW)}-1 a, and {Ag(SbW)}-2) via a facile one-pot solvothermal approach. Among them, for the first time, an unprecedented isomeric {Ag} nanoclusters are obtained in polyoxoanions {Ag(SbW)}-1 and {Ag(SbW)}-2, which should be probably induced by the different distribution of coordinating O atoms in two isomeric bowl-like {SbW} ligands. Clusters {Ag(SbW)}-1 and {Ag(SbW)}-2 exhibit distinct electronic structures and physicochemical properties due to the different geometric structures of the {Ag} nanoclusters, but both clusters can effectively catalyze the visible-light-driven hydrogen evolution with over 22,000 turnovers (TONs) after 6-hour photocatalysis.