A new polyoxovanadium cluster compound, [VO{(OCHCH)N(CHCHOH)}]·0.5CHCN, was synthesized and characterized by single-crystal X-ray diffraction analysis, FTIR and UV-vis spectroscopy, and TGA. The cluster is composed of a fully reduced cyclic {VNO} framework, which adopts an Anderson-like structure and is comprised of a ring of six edge-sharing {VON} octahedra incorporating six {(OCHCH)N(CHCHOH)} ligands. Two (OCHCH-) arms of each of the six triethanolamine ligands are directly incorporated into the oxometalate core and the third {-CHCHOH} arm remains pendant. In the condensed phase, the clusters form discrete hcp layers through inter-cluster hydrogen bonding. These layers stack through soft chemical interactions to form a 3D network structure. The neutral cluster, [VO{(OCHCH)N(CHCHOH)}], is the isopolyoxovanadium analogue to the cationic clusters contained in a series of heteropolyoxovanadium compounds previously introduced by our laboratory, e.g., [LiVO{(OCHCH)N(CHCHOH)}]; its existence shows that a heteroatom is not required to form or stabilize the common organofunctionalized vanadium oxide framework: [VO{(OCHCH)N(CHCHOH)}]. To the best of our knowledge, the isopolyoxovanadium and heteropolyoxovanadium clusters represent the first reported isopoly-heteropoly analogues in the polyoxometalate field. We compare the TGA profile, FTIR and UV-vis spectra of the new compound with two of its cationic heteropoly analogues.
A new diethanolamine functionalized oxovanadium cationic cluster was synthesized and characterized; electrochemical and UV-vis absorption properties are consistent with two distinct MLCT processes.
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.
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