A platonic solid templating Archimedean solid: an unprecedented nanometre-sized Ag-37 cluster

The spontaneous formation of discrete spherical nanosized molecules is prevalent in nature, but the authentic structural mimicry of such highly symmetric polyhedra from edge sharing of regular polygons has remained elusive. Here we present a novel ball-shaped {(HNEt3)[Ag37S4((SC6H4Bu)-Bu-t)(24)(CF3COO)(6)(H2O)(12)]} cluster (1) that is assembled via a one-pot process from polymeric {(HNEt3)(2)[Ag-10((SC6H4Bu)-Bu-t)(12)]}(n) and CF3COOAg. Single crystal X-ray analysis confirmed that 1 is a T-d symmetric spherical molecule with a [Ag-36((SC6H4Bu)-Bu-t)(24)] anion shell enwrapping a AgS4 tetrahedron. The shell topology of 1 belongs to one of 13 Archimedean solids, a truncated tetrahedron with four edge-shared hexagons and trigons, which are supported by a AgS4 Platonic solid in the core. Interestingly, the cluster emits green luminescence centered at 515 nm at room temperature. Our investigations have provided a promising synthetic protocol for a high-nuclearity silver cluster based on underlying geometrical principles.