A classical [V 10 O 28 ] 6- 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 in situ generated classical [V 10 O 28 ] 6- core and Ag 50 shell, constrained by the S- and O-donor ligands with a specific distribution. Such {V 10 O 28 @Ag 50 } structure displays geometric inheritance from the D 2h 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.