New Types of Heterospin Complexes from trans-Oxamido-Bridged Copper(II) Binuclear Units and Nitronyl Nitroxide Radicals:  Crystal Structure and Magnetic Characterization

Three new heterospin complexes derived from trans-oxamido-bridged copper(II) binuclear units [Cu(2)(oxen), oxen = N,N-bis(2-aminoethyl)oxamide] and pyridine-substituted nitronyl nitroxides (o-, m-, and p-PYNN) were synthesized and characterized structurally and magnetically. Complexes 1 and 2 are four-spin complexes. Interestingly, it is found that in complex 3, the Cu(II) ions and m-PYNN units are arranged to form 1D double-stranded helical chains, which to the best of our knowledge is the first example of a metal nitronyl nitroxide complex with such a 1D helical structure. The temperature dependencies of the magnetic susceptibilities of 1 and 2 were fitted to the four-spin model with the Hamiltonian H = -2Js(Cu1)s(Cu2) - 2j(s(Cu1)s(rad1) - s(Cu2)s(rad2)), leading to J = -150.5 cm(-)(1) and j = 47.2 cm(-)(1) for complex 1 and J = -191.7 cm(-)(1) and j = -18.9 cm(-)(1) for complex 2. The temperature dependence of the magnetic susceptibility of complex 3 was approximately simulated with a simple model composed of a dimer of Cu(II) ions and two m-PYNN molecules. The best fitting leads to the values of J = -183.0 cm(-)(1) and zJ' = -0.55 cm(-)(1) for the magnetic exchange of two Cu(II) ions through the oxamide bridge and that between the dimer of Cu(II) ions and two m-PYNN molecules, respectively. The antiferromagnetic exchange of oxamido-bridged Cu(II) ions in complexes 1-3 is strong. The strength of such antiferromagnetic interactions is also similar for the three complexes.