Luminescent Molecular Ag−S Nanocluster [Ag₆₂S₁₃(SBu^<i>t</i>)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 [Ag48(SBut)32] shell via both Ag−S bonds and Ag···Ag interactions. This novel cluster displays intense red emission in both the solid state and solution at room temperature.