Structural Isomerism of {Ag<sub>14</sub>}<sup>10+</sup> Nanocluster Encapsulated by Bowl‐like Polyoxometalates
Manzhou Chi, Jianyu Wei, Zichen Zhao, Xiaoyi Liu, Wanting Sun, Yeqin Feng, Hongjin Lv, Guo‐Yu Yang, Guo‐Yu Yang
Abstract
Abstract 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 14 (Sb 3 W 30 ) 2 }‐1 , {Ag 14 (Sb 3 W 30 ) 2 }‐1 a , and {Ag 14 (Sb 3 W 30 ) 2 }‐2 ) via a facile one‐pot solvothermal approach. Among them, for the first time, an unprecedented isomeric {Ag 14 } 10+ nanoclusters are obtained in polyoxoanions {Ag 14 (Sb 3 W 30 ) 2 }‐1 and {Ag 14 (Sb 3 W 30 ) 2 }‐2 , which should be probably induced by the different distribution of coordinating O atoms in two isomeric bowl‐like {Sb 3 W 30 } ligands. Clusters {Ag 14 (Sb 3 W 30 ) 2 }‐1 and {Ag 14 (Sb 3 W 30 ) 2 }‐2 exhibit distinct electronic structures and physicochemical properties due to the different geometric structures of the {Ag 14 } 10+ nanoclusters, but both clusters can effectively catalyze the visible‐light‐driven hydrogen evolution with over 22,000 turnovers (TONs) after 6‐hour photocatalysis.