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.

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