In this paper the reaction products of the basic gold(I) species [Au(C6Cl5)(2)](-) against the acid salt Ag(OClO3) in the presence of the S-donor macrocyclic ligand 1,4,7-trithiacyclononane ([9]aneS(3)) are studied in different solvents. Two different isomers of stoichiometry [{Au(C6C15)(2)}Ag([9]aneS(3))](2) were isolated depending on the solvent used, dichloromethane or tetrahydrofuran, which show different luminescence in the solid state. X-ray diffraction studies of these compounds reveals that both show the same heteropolynuclear Ag center dot center dot center dot Au center dot center dot center dot Au center dot center dot center dot Ag system but with different Au center dot center dot center dot Au interaction distances and different relative positions of the cationic fragment [Ag([9]aneS(3))](+) in the structure with respect the bimetallic Au center dot center dot center dot Au core. This work includes a study of the optical properties of both isomers, as well as time-dependent density functional theory calculations that were performed to determine the origin of their different luminescence.