Affiliation:
1. Department of Chemistry Illinois Institute of Technology Chicago IL 60616 USA
2. ChemMatCARS The University of Chicago Lemont IL 60439 USA
3. Department of Chemistry Boston University Boston MA 02215 USA
Abstract
AbstractOrganofunctionalized 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 have been prepared by solvothermal reactions. The new oxo‐alkoxide compounds were 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.
Subject
General Chemistry,Catalysis,Organic Chemistry
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