A Controlled Route to a Luminescent 3 d10-5 d10 Sulfido Cluster Containing Unique AuCu2(μ3-S) Motifs

The first examples of gold(I) trimethylsilylchalcogenolate complexes were synthesized and their reactivity showcased in the preparation of a novel gold–copper–sulfur cluster [Au4Cu4S4(dppm)2] (dppm=bis(diphenylphosphino)methane). The unprecedented structural chemistry of this compound gives rise to interesting optoelectronic properties, including long‐lived orange luminescence in the solid state. Through time‐dependent density functional theory calculations, this emission is shown to originate from ligand‐to‐metal charge transfer facilitated by Au⋅⋅⋅Cu metallophilic bonding. All that glitters is not (only!) gold: The triphenylphosphine‐ligated gold(I) trimethylsilylchalcogenolate complexes (Ph3PAu‐ESiMe3; E = S, Se) were synthesized and their reactivity highlighted with the selective preparation of the gold–copper–sulfur cluster [Au4Cu4S4(dppm)2] (dppm=bis(diphenylphosphino)methane). The cluster is comprised of [(μ3‐S)CuAu2]+ units; the structural chemistry of this compound gives rise to interesting photophysical properties, including long‐lived orange luminescence in the solid state.