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.
Keywords: Structural isomerism * Silver nanocluster * Polyoxometalates * Photothermal conversion * Photocatalytic hydrogen evolution.
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