A series of heterobimetallic complexes [((VO)-O-IV)L1Cu(II)(mu-OAC)(MeOH)](ClO4) (1) and [((VO)-O-IV)L1M(II)(mu-OAc)(H2O)](ClO4). H2O (M = Ni (2), Co (3), Fe (4), Mn (5)) derived from a symmetric tetraaminodiphenol macrocyclic ligand H(2)L1 have been synthesized and characterized. The crystal structure of 1 has been determined. The complex (C27H41N4O10ClCuV) crystallizes in the monoclinic space group P2(1)/c with a = 13.227(3) Angstrom, b = 14.932(3) Angstrom, c = 17.019(3) Angstrom, beta = 112.29(1)degrees, and Z = 4. Both the metal centers in 1 are six-coordinated and are triply bridged by the two phenolate and the acetate oxygens; the sixth coordination site of the copper atom is occupied by a distantly placed methanol oxygen (Cu-O = 2.452(5) Angstrom), while that of the vanadium by the oxo oxygen (V-O = 1.627(4) Angstrom). The metal centers are separated by 3.066(1) Angstrom, and the dihedral angle (a) between the metal planes is 32.0 degrees. Variable-temperature (4-300 K) magnetic susceptibility measurements of 1-5 and of [((VO)-O-IV)L2Cu(II)(mu-OAc)(H2O)](ClO4) (6) (where H(2)L2 is an asymmetric tetraaminodiphenol macrocyclic ligand) have been made and treated with the spin-Hamiltonian H = -2/S-1.S-2 All the complexes, except 5, exhibit ferromagnetic exchange interaction with the following values of J (in cm(-1)) : 42.5 (1), 12.0 (2), 4.4 (3), 4.4 (4), and 46.0 (6); complex 5 behaves antiferromagnetically with J = -14.2 cm(-1). A linear correlation between J and A has been proposed for (CuVO)-V-II-O-IV complexes.