A Superatomic {Ag₈}⁶⁺ Cluster Induced by Asymmetric Mixed-Addendum Polyoxometalate

Polyoxometalate (POM)-encapsulated Ag nanoclusters have attracted increasing research interest due to their intriguing structural diversities and synergistic catalytic properties; however, the types of POM ligands are limited to the multidentate lacunary or ring-shaped POMs. Herein, we develop an asymmetric POM-induced synthetic strategy to synthesize a superatomic {Ag 8 } 6+ cluster encapsulated by six redox-active mixed-addendum P 2 W 15 Nb 3 ligands, (C 16 H 36 N) 6 Na 4 H 24 [Na 2 Ag 8 (P 2 W 15 Nb 3 O 61 ) 6 ]·36CH 3 CN ( {Ag 8 @(P 2 W 15 Nb 3 ) 6 } ). The oriented aggregation of Ag + ions is attributed to the unevenly distributed electron density over the asymmetric mixed-addendum P 2 W 15 Nb 3 ligands. The resulting {Ag 8 @(P 2 W 15 Nb 3 ) 6 } cluster exhibits interesting photothermal and photocatalytic performance due to the redox activity of P 2 W 15 Nb 3 ligands. This work presents a new research avenue for the construction of Ag nanoclusters induced by asymmetric all-inorganic POM ligands and will stimulate the structural exploration and catalytic applications of atomically precise metal nanoclusters.