Abstract

The reactions of complex [Fe2Ni(O)(Piv)6(Et2O)(H2O)2] (1) with 1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy) gave the following new coordination compounds: the trinuclear complex [Fe2Ni(O)(Piv)6(phen)H2O]·(C2H5)2O (2), the tetranuclear ones [Fe2Ni2(OH)2(Piv)8(phen)2] (3) and [Fe2Ni2(OH)2(Piv)8(bpy)2] (4), depending on the crystallization conditions. According to single crystal X-ray diffraction data, all the compounds have molecular structures. The Mössbauer spectra of 1–3 correspond to high-spin Fe3+ ions in an octahedral environment consisting of oxygen atoms. The DC magnetic susceptibility studies and quantum-chemical analysis of intra- and intermolecular J pathways using broken-symmetry density functional theory (DFT) showed that all exchange interactions in tri- (1, 2) and tetranuclear (3) complexes are antiferromagnetic. The exchange coupling is weaker in 3 due to the lower ability of the bridging OH-groups to mediate superexchange. Thermal destruction processes have been studied for 2 and 3. The final products of thermolysis are the mixed oxide NiFe2O4.

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