A Controlled Route to a Luminescent 3 d -5 d Sulfido Cluster Containing Unique AuCu (μ -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 [Au Cu S (dppm) ] (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.