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 {Ag₈}⁶⁺ cluster encapsulated by six redox-active mixed-addendum P₂W₁₅Nb₃ ligands, (C₁₆H₃₆N)₆Na₄H₂₄[Na₂Ag₈(P₂W₁₅Nb₃O₆₁)₆]·36CH₃CN ({Ag₈@(P₂W₁₅Nb₃)₆}). The oriented aggregation of Ag⁺ ions is attributed to the unevenly distributed electron density over the asymmetric mixed-addendum P₂W₁₅Nb₃ ligands. The resulting {Ag₈@(P₂W₁₅Nb₃)₆} cluster exhibits interesting photothermal and photocatalytic performance due to the redox activity of P₂W₁₅Nb₃ 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.