title: Organo-functionalized metal-oxide clusters: synthesis and characterization of the reduced cationic species [NaV(IV)6O6{(OCH2CH2)2NH}6]+.
abstract: A new heteropolyoxovanadium compound, [NaV6O6{(OCH2CH2)2NH}6]·(OH)0.5Cl0.5·3(H2O), was synthesized and characterized by single-crystal X-ray diffraction analysis, cyclic voltammetry, FTIR and UV-vis spectroscopy, and TGA. [NaV6O6{(OCH2CH2)2NH}6]·(OH)0.5Cl0.5·3(H2O) contains the diethanolamine functionalized oxovanadium cationic cluster, [NaV(IV)6O6{(OCH2CH2)2NH}6](+). The cluster cation is composed of a fully reduced cyclic {NaV6N6O18} framework which adopts an Anderson-like structure and is comprised of a ring of six edge-sharing {VO5N} octahedra linked to a central {NaO6} unit. Two (OCH2CH2-) arms of each of the six diethanolamine ligands are incorporated into the oxometalate core. FTIR spectra are consistent with the presence of expected V=Ot stretching modes and functionalization with diethanolamine. Electrochemical and UV-vis absorption properties are consistent with two distinct MLCT processes: the characteristic V=Ot dπ-pπ interaction, and a second process occurring through the hydrogen-terminated nitrogen atoms (V-N-H) of the octahedra forming the cyclic {NaV6N6O18} core.
authors.affiliation: Department of Biological and Chemical Sciences, Illinois Institute of Technology, Chicago, IL 60616, USA. khan@iit.edu.
authors.forename: M Ishaque
authors.initials: MI
authors.lastname: Khan
authors.forename: Y
authors.initials: Y
authors.lastname: Zheng
authors.forename: H
authors.initials: H
authors.lastname: Li
authors.forename: L
authors.initials: L
authors.lastname: Swenson
authors.forename: A
authors.initials: A
authors.lastname: Basha
authors.forename: R J
authors.initials: RJ
authors.lastname: Doedens