The one-electron oxidized linear pentanuclear nickel complexes [Ni-5(tpda)(4)(H2O)(BF4)](BF4)(2) (1) and [Ni-5(tpda)(4)(SO3CF3)(2)](SO3CF3) (2) have been synthesized by reacting the neutral compound [Ni-5(tpda)(4)Cl-2] with the corresponding silver salts. These compounds have been characterized by various spectroscopic techniques. Compound 1 crystallizes in the monoclinic space group P2(1)/n with a = 15.3022(1) Angstrom, b = 31.0705(3) Angstrom, c = 15.8109(2) Angstrom, = 92.2425(4), V = 7511.49(13) Angstrom(3), Z = 4, and compound 2 crystallizes in the monoclinic space group C2/c with a = 42.1894(7) Angstrom, b = 17.0770(3) Angstrom, c = 21.2117(4) Angstrom, p = 102.5688(8), V = 14916.1(5) Angstrom(3), Z = 8. X-ray structural studies reveal an unsymmetrical Ni-5 unit for both compounds 1 and 2. Compounds 1 and 2 show stronger Ni-Ni interactions as compared to those of the neutral compounds.