Luminescent Molecular Ag-S Nanocluster [Ag62S13(SBut)32](BF4)4

The first observation of luminescence from a structurally well-defined Ag2S molecular nanocluster is reported. Reaction of AgSBut/AgBF4 with N2H4 in methanol affords the tetracationic cluster [Ag62S13(SBut)(32)](BF4)(4), which has a core-shell configuration. The 14 silver(I) centers of the [Ag14S13] core are in a face-centered cubic arrangement with each edge bridged by a S2- ligand; the core is further connected to the [Ag-48(SBut)(32)] shell via both Ag-S bonds and Ag center dot center dot center dot Ag interactions. This novel cluster displays intense red emission in both the solid state and solution at room temperature.