Reaction of the PNNP ligand system N,N'-bis[(2-diphenylphosphino)phenyl]formamidinate (dpfam) featuring different coordination compartments with [AuCl(tht)], [CuMes]5, [AgMes]4, or [AuC6F5(tht)] (tht = tetrahydrothiophene) resulted in tetranuclear homo- and heterometallic coinage metal complexes, as well as a hexanuclear gold complex. All of them feature a metal string conformation. Photophysical investigation revealed a significant dependence of the photoluminescence properties on the metal composition. Below 100 K, the PL efficiency of three compounds approaches nearly 100%.