Organo-Functionalized Lacunary Double Cubane Type Oxometallates: Synthesis, Structure, and Properties of [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (M = Co, Zn)

Organofunctionalized tetranuclear clusters [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (1, M = Co; 2, M = Zn) containing an unprecedented oxometallacyclic {M2V2Cl2N4O8} (M = Co, Zn) framework are prepared by solvothermal reactions. The new oxo-alkoxide compounds are fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab-initio computational methods, and complete single crystal X-ray diffraction structure analysis. The isostructural clusters are formed of edge-sharing octahedral {VO5N} and trigonal bipyramidal {MO3NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of 1 and 2 in an unusual two-mode fashion, unobserved previously. In the crystalline state, the clusters of 1 and 2 are joined by hydrogen-bonds to form a three-dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [Jiso(VIV-VIV) = -5.4(1); -3.9(2) cm-1], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [Jiso (VIV-CoII) = -12.6 and -7.5 cm-1] contained in 1.