A classical [VO] anion templated high-nuclearity silver thiolate cluster.

Polyoxovanadates (POVs) as templates are still scarcely observed in silver clusters. Herein, the largest known POV-based silver cluster (Ag50) was synthesized, which is a core-shell conformation composed of the generated classical [VO] core and Ag shell, constrained by the S- and O-donor ligands with a specific distribution. Such {VO@Ag} structure displays geometric inheritance from the symmetric decavanadate to the silver skeleton. The solution behavior, solid-state stability and photoelectric properties are discussed in detail. This work provides enlightenment for the further construction of POV-templated high-nuclearity silver clusters.