A platonic solid templating Archimedean solid: an unprecedented nanometre-sized Ag37 cluster

Abstract

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(SC₆H₄^tBu)₂₄(CF₃COO)₆(H₂O)₁₂]} cluster (1) that is assembled via a one-pot process from polymeric {(HNEt₃)₂[Ag₁₀(SC₆H₄^tBu)₁₂]}_n and CF₃COOAg. Single crystal X-ray analysis confirmed that 1 is a T_d symmetric spherical molecule with a [Ag₃₆(SC₆H₄^tBu)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.