The reaction of [Rh(mu-PyS2)(2)(cod)(4)] (PyS2 = 2,6-pyridinedithiolate, cod = 1,5-cyclooctadiene) with CF3SO3Me gave the cationic complex [Rh-4(mu-PyS2Me)(2)(cod)(4)][CF3SO3](2) (1) with two 6-(thiomethyl)pyridine-2-thiolate bridging ligands from the attack of Me+ at the terminal sulfur atoms of the starting material. Under identical conditions [Rh-4(mu-PyS2)(2)(tfbb)(4)] (tfbb = tetrafluorobenzobarrelene) reacted with CF3SO3Me to give the mixed-ligand complex [Rh-4(mu-PyS2)(mu-PyS2Me)(tfbb)(4)][CF3SO3] (2). The nucleophilicity of the bridging ligands in the complexes [Rh-4(mu-PyS2)(2)(diolefin)(4)] was exploited to prepare heteropolynuclear species. Reactions with [Au(PPh3)(Me2CO)]-[ClO4] gave the hexanuclear complexes [(PPh3)(2)Au2Rh4(mu-PyS2)(2)(diolefin)(4)][ClO4](2) (diolefin = cod (3), tfbb (4)). The structure of 4, solved by X-ray diffraction methods, showed the coordination of the [Au(PPh3)](+) fragments to the peripheral sulfur atoms in [Rh-4(mu-PyS2)(2)(diolefin)(4)] along with their interaction with the neighbor rhodium atoms. Neutral coordination polymers of formula [CIMRh4(mu-PyS2)(2)(diolefin)(4)](n) (M = Cu (5, 6), Au (7)) result from the self-assembly of alternating [Rh-4(mu-PyS2)(2)(diolefin)(4)] ([Rh-4]) blocks and MCl linkers. The formation of the infinite polymetallic chains was found to be chiroselective for M = Cu; one particular chain contains exclusively homochiral [Rh-4] complexes. Cationic heterometallic coordination polymers of formula [MRh4(mu-PyS2)(2)(diolefin)(4)],[BF4](n) (M = Ag (8, 9), Cu (10, 11)) and [Rh-5(mu-PyS2)(2)(diolefin)(5)](n)[BF4](n) (12, 13) result from the reactions of [Rh-4] with [Cu(CH3CN)(4)]BF4, AgBF4, and [Rh(diolefin)(Me2CO)(2)]BF4, respectively. The heterometallic coordination polymers exhibit a weak electric conductivity in the solid state in the range (1.2-2.8) x 10(-7) S cm(-1).