Polynuclear heterovalent Au-III-M-I (M = Cu, Ag, Au) cluster complexes [AU(III)CU(8)(I)(mu-dppm)(3)(tdt)(5)](+) (1), [(Au3Ag8I)-Ag-III(mu-dppm)(4)(tdt)(8)](+) (2), and [(AuAu4I)-Au-III(mu-dPPM)(4)(tdt)(2)](3+) (3) were prepared by reaction of [Au-III(tdt)(2)](-) (tdt = toluene-3,4-dithiolate) with 2 equiv of [M-2(I)(dPPM)(2)](2+) (dppm = bis(diphenylphosphino) methane). Complex 3 originates from incorporation of one [Au-III(tdt)(2)](-) with two [Au-2(I)(dPPM)(2)](2+) components through Au-III-S-Au-I linkages. Formation of complexes 1 and 2, however, involves rupture of metal-ligand bonds in the metal components and recombination between the ligands and the metal atoms. The Au(tdt)2 component connects to four M-I atoms through Au-III-S-M-I linkages in syn and anti conformations in complexes 1 (M = Cu) and 3 (M = Au), respectively, but in both syn and anti conformations in complex 2 (M = Ag). The tdt ligand exhibits five types of bonding modes in complexes 1-3, chelating Au-III or M-I atoms as well as bridging Au-III-M-I or M-I-M-I atoms in different orientations. Although complexes 1 and 2 are nonemissive, Au-III Au-4(I) Complex 3 shows room-temperature luminescence with emission maximum at 555 nm (tau(em) = 3.1 mu s) in the solid state and at 570 nm (tau(em) = 1.5 mu s) in acetonitrile solution.