The treatment of a slurry of an equimolar mixture of [Sn(edt)(2)] (edt = ethane-1,2-dithiolate) and [Et4N]Cl center dot xH(2)O with Cul in the presence of PPh3 gave a tetranuclear compound, [Sn(edt)(2)Cl(mu-I)(,mu(3)-I)(CUPPh3)(3)] (1), which consists of a rectangular-pyramidal [Sn(edt)(2)Cl](-) moiety ligated by three [Cu(PPh3)](+) fragments via the sulfur atoms of the edt(2-) ligands. The treatment of a slurry of [Sn(edt)(2)] and excess [Et4N]Br with [Cu(MeCN)(4)][PF6] in the presence of PPh3 afforded a pentanuclear compound, [Sn(edt)(2)(mu-Br)(2)(mu(3)-Br)(2)(CUPPh3)(4)] (2), which comprises two [(CuPPh3)(2)(-)(mu-Br)](+) fragments symmetrically ligating an octahedral trans- [Sn(edt)(2) Br-2](2-) moiety via the sulfur and bromide atoms. Reaction of [Sn(edt)(2)] with [Cu(MeCN)(4)][PF6] and PPh3 in a mixed MeCN/CH2Cl2 solution yielded a novel octanuclear compound, [{Sn(edt)(2)}(3)(mu-OH)(3)CU5(PPh3)(8)][PF6](2) (3), which may be described as a triangular [{Sn(edt)(2)}(3)(mu-OH)(3)](3-) core chelated by three [Cu(PPh3)(2)](+) species and capped by two [Cu(PPh3](+) species. The luminescent properties of compounds 1, 2, and 3 were investigated in a CH2Cl2 solution at room temperature. Upon excitation at lambda > 360 nm, these compounds are luminescent in CH2Cl2 solution with emissions having maxima at 422, 515, and 494 nm, respectively.