Miscellaneous tetrasubstituted ammonium salts of [Pt 3n -(CO) 6n ]2-(n = 5-8) clusters, obtained by the stoichiometric oxidation of the corresponding [Pt 9 (CO) 18 ] 2-salts with tropylium tetrafluoroborate, self-assemble into infinite semicontinuous or continuous {[Pt 3n (CO) 3n (µ-CO) 3n ] 2-} ϱ conductor wiresOne dimensional molecular metal wires [1,2] and one-and two-dimensional superclusters that are assembled through M-M bonds [3,4] are interesting as low-dimensional molecular materials, and they may find applications in molecular electronics and nanolithography. [5][6][7] According to EHMO calculations, the LUMO of a Pt 3 (CO) 3 (µ-CO) 3 triangular moiety involves the combination of cyclopropenyl-like inphase Pt p z atomic orbitals. [8,9] For an infinite stack of neutral Pt 3 (CO) 3 (µ-CO) 3 or dianionic [Pt 3 (CO) 3 (µ-CO) 3 ] 2-moieties, the σMO band, which is generated along the C 3 axis by the cyclopropenyl-like MOs, should be empty or completely filled, respectively. Therefore, such a stack should not be stable. However, in the case where the stack is generated by the assembly of [Pt 3n (CO) 6n ] 2-(n Ͼ 1) cluster dianions, the above MO band would only be 1/n filled; therefore, the stack could be feasible and may behave as a conducting molecular wire.The first hint of a possible strategy that might favor selfassembly of [Pt 3n (CO) 2-dianions, it appeared more appropriate to substitute r -with the length of the dianion (L), and consequently, to replace r + by the diameter of the cation (D), and to use the L/D ratio as a rough guideline to achieve self-assembly of the dianions. In particular, it was speculated that a high L/D ratio would imply a great difference between the sizes of the dianion and the cation and a decreased repulsion between the dianions; the constant 2-charge would be delocalized over an increasing number of Pt 3 (CO) 6 units. Furthermore, in the case of self-assembly of continuous [Pt 3n (CO) 6n ] 2-stacks, L would also determine the amount of filling of the σMO band that develops along the C 3 axis.We have, therefore, reinvestigated the synthesis and structures of miscellaneous [NR 4 ] 2 [Pt 3n (CO) 6n ] salts to assess the effect of the L/D ratio on self-assembly. We report here some significant structural results, as well as preliminary resistivity measurements of the above salts, which point out that stacking of [Pt 3n (CO) 6n ] 2-dianions leads to conducting molecular wires.The investigated salts are collected in 2-salt [13] with tropylium tetrafluoroborate and crystallized from THF/toluene or acetone/2-propanol mixtures. The formulas of miscellaneous salts were established