New oximate-bridged tetranuclear nickel(II) complexes of compositions {Ni(Dien)}2(μ3-OH)2{Ni2(Moda)4}(ClO4)2·Solv (Solv = H2O, 1a; Solv = 2CH3NO2, 1b; Solv = 2H2O·2C4H8O2, 1c), {Ni(Sdien)}2(μ3-OH)2{Ni2(Moda)4}(ClO4)2·H2O (2), {Ni(Odien)}2(μ3-OH)2{Ni2(Moda)4}(ClO4)2·0.6H2O (3), {Ni(Dien)}2(μ3-OH)2{Ni2(Inaf)4}(ClO4)2·CH3NO2 (4) and {Ni(Odien)}2(μ3-OH)2{Ni2(Inaf)4}(ClO4)2·2NaClO4·2H2O (5) and the dinuclear complex (Ni{Odien})2(Moda)2(ClO4)2 (6) have been prepared (Dien = 1,5-diamino-3-azapentane, Odien = 1,5-diamino-3-oxapentane, Sdien = 1,5-diamino-3-thiapentane, ModaH = butane-2,3-dione monooxime, InafH = phenylglyoxaldoxime). X-ray examination revealed similar structures for 1a, 1b, 1c, 2 and 3, with a rhombic “chair” (out-of-phase “butterfly”) arrangement of the four nickel(II) atoms and two hydroxo-bridges. The complexes were examined by magnetochemistry, UV-VIS spectroscopy and voltammetry. 1–3 display antiferromagnetic coupling of the central with the terminal nickel(II) atoms and ferromagnetic spin alignment between the central nickel(II) atoms. In contrast, all the spin exchanges in 4 and 5 were found to be antiferromagnetic, as is the coupling in dinuclear 6.
