Organo‐Functionalized Lacunary Double Cubane‐Type Oxometallates: Synthesis, Structure, and Properties of [(M^IICl)₂(V^IVO)₂{((HOCH₂CH₂)(H)N(CH₂CH₂O))(HN(CH₂CH₂O)₂)}₂] (M=Co, Zn)

Abstract

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.