Mixtures of silver salts AgX (X = NO3 , CF3 CO2 , CF3SO3) with M[Au(C6F5)2] (M = NBu4, PPh4) gave respectively the ionic mixed-metal clusters [M2{(C6F5)4Au2Ag2X2}] n (1, X = NO3 ; a, M = NBu4 ; b, M = PPh4) and [M{(C6F5)4Au2Ag2X}]n , (2a,b, X = CF3 CO2 ; 3a,b, X = CF3SO 3). The degree of aggregation n of these cluster compounds depends strongly on the method of isolation (solvent evaporation or precipitation); for example, recrystallization of 1a gave a crystalline salt of the tetraanion [(C6F5)4Au2Ag2X2]2 4− as well as the polymer [(NBu4)2{(C6F5)4Au2Ag2(NO3)2 }]n . The aurophilic Au···Au interactions strongly influence the photoemission wavelength. The anion X has remarkably little effect on the luminescence color but strongly influences the conformation of the polyanionic chains, leading to a variety of solid-state structures, from well-defined dimers (1a 1) to linear (1b) and curved (1a 2 , 2a) polymeric chain aggregates. ■