Reactions of Pt(diimine)(tdt) (tdt =3,4-toluenedithiolate) with [M(2)(dppm)(2)(MeCN)(2)](2+) (M = Cu(I) or Ag(I), dppm = bis(diphenylphosphino)methane) gave heterotrinuclear complexes [PtCu(2)(tdt)(mu-SH)(dppm)(3)](ClO(4)) (1) and [PtCu(2)(diimine)(2)(tdt)(dppm)(2)](ClO(4))(2) (diimine = 2,2'-bpyridine (bpy) 2; 4,4'-dimethyl-2,2'-bipyridine (dmbpy) 3; phenanthroline (phen) 4, 5-bromophenanthroline (Brphen) 5) for M = Cu(I), but [PtAg(2)(tdt)(mu-SH)(dppm)(3)](SbF(6)) (6) and [PtAg(2)(diimine)(tdt)(dppm)(2)](SbF(6))(2) (diimine = bpy 7; dmbpy 8; phen 9; Brphen 10) for M = Ag(I). While the complexes [PtAg(2)(diimine)(tdt)(dppm)(2)](SbF(6))(2) (7-10) result from linkage of Pt(diimine)(tdt) and [M(2)(dppm)(2)(MeCN)(2)](2+) by tdt sulfur donors, formation of [PtCu(2)(diimine)(2)(tdt)(dppm)(2)](ClO(4))(2) (2-5) is related to rupture of metal-ligand bonds in the metal components and recombination between the ligands and the metal atoms by self-assembly. The formation of 1 and 6 is involved not only in dissociation and recombination of the metal components, but also in disruption of C-S bonds in the dithiolate (tdt). The dithiolate tdt adopts a chelating and bridging coordination mode in anti conformation for [PtCu(2)(diimine)(2)(tdt)(dppm)(2)](ClO(4))(2) (2-5), whereas there is the syn conformation for other complexes. Compounds 1 and 6 represent sparse examples of mu-SH-bridged heterotrinuclear Pt(II)M(I)(2) complexes, in which Pt(II)-M(I) centers are bridged by dppm and sulfur donors of tdt, whereas M(I)-M(I) (M = Cu for 1; Ag for 6) centers are linked by dppm and the mu-SH donor. The (31)P NMR spectra show typical platinum satellites (J(Pt-P) = 1450-1570 Hz) for 1-6 and Ag-P coupling for Pt(II)-Ag(I) (J(Ag-P) = 350-450 Hz) complexes 6-10. All of the complexes show intense emission in the solid state and in frozen glasses at 77 K. The complexes [PtAg(2)(diimine)(tdt)(dppm)(2)](SbF(6))(2) (7-10) also afford emission in fluid acetonitrile solutions at room temperature. Solid-state emission lifetimes at room temperature are in the microsecond range. It is revealed that emission energies of the trinuclear heterometallic complexes [PtAg(2)(diimine)(tdt)(dppm)(2)](SbF(6))(2) (7-10) exhibit a remarkable blue shift (0.10-0.35 eV) relative to those of the precursor compounds Pt(diimine)(tdt). The crystal structures of 1, 2, 4, 6, 8, and 9 were determined by X-ray crystallography.

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