Structural Isomerism of {Ag14}10+ 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 {Ag14(Sb3W30)2}‐1, {Ag14(Sb3W30)2}‐1a, and {Ag14(Sb3W30)2}‐2) via a facile one‐pot solvothermal approach. Among them, for the first time, an unprecedented isomeric {Ag14}10+ nanoclusters are obtained in polyoxoanions {Ag14(Sb3W30)2}‐1 and {Ag14(Sb3W30)2}‐2, which should be probably induced by the different distribution of coordinating O atoms in two isomeric bowl‐like {Sb3W30} ligands. Clusters {Ag14(Sb3W30)2}‐1 and {Ag14(Sb3W30)2}‐2 exhibit distinct electronic structures and physicochemical properties due to the different geometric structures of the {Ag14}10+ nanoclusters, but both clusters can effectively catalyze the visible‐light‐driven hydrogen evolution with over 22,000 turnovers (TONs) after 6‐hour photocatalysis.