A new design concept has been realized for the construction of molecular conductors, whereby the building unit contains a core reservoir of carriers made up of metal ions with controllable valence states and shelled by flat organic ligands having an extended pi-system to promote supramolecular electronic communication. Therefore, reacting the conjugated multidentate ligand 5,5'-pyridy1-3,3'-bi-1H-pyrazole with different copper salts solvothermally led to three interesting hexameric salts having different ground-state valences, [Cu-6(II)(L)(4)(NO3)(CH3OH)(2)](NO3)(3)center dot 4CH(3)OH, [(CH3)(2)NH2][(CuCu5II)-Cu-I(L)(4)](SO4)(2)center dot 4H(2)O, and [(Cu2Cu4II)-Cu-I(L)(4)](NO3)(2)center dot 2CH(3)OH. The monovalent Cu-6(II) salt is an insulator, but the mixed-valent Cu-5(II)-Cu-I and Cu-4(II)-Cu-2(I) salts are semiconductors. Magnetic exchange interactions up to J(NN) = -158 cm(-1) dominate the susceptibilities and lead to ground-state spin S-T = 1 (Cu-6(II)), 1/2 (Cu-5(II)-Cu-I), and 0 (Cu-4(II)-Cu-2(I)) at 40 K. Cyclic voltammetry shows the stepwise one-electron oxidation-reduction through all the possible valence states. The theoretical calculations of the electronic and band structures of the three compounds substantiate the experimentally observed physical properties.