An organo-functionalized metal–oxide cluster, [VIV6O6{(OCH2CH2)2N(CH2CH2OH)}6], with Anderson-like structure. Issue 41 (27th September 2016)

• Record Type: Journal Article
• Authors: Li, H.; Swenson, L.; Doedens, R. J.; Khan, M. I.
• Is Part Of: Dalton transactions. Volume 45:Issue 41(2016)
• Page Start: 16511
• Page End: 16518
• Publication Date: 2016-09-27
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt03354g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The polyoxovanadium cluster compound, [VIV6O6 {(OCH2 CH2 )2 N(CH2 CH2 OH)}6 ], is the isopolyoxovanadium analogue to cationic heteropolyoxovanadium species, such as [MVIV6O6 {(OCH2 CH2 )2 N(CH2 CH2 OH)}6 ] + (M = Li, Na). These isopolyoxovanadium and heteropolyoxovanadium clusters represent the first reported isopoly-heteropoly analogues in the polyoxometalate field. Abstract : A new polyoxovanadium cluster compound, [VIV6O6 {(OCH2 CH2 )2 N(CH2 CH2 OH)}6 ]·0.5CH3 CN, 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 {V6 N6 O18 } framework, which adopts an Anderson-like structure and is comprised of a ring of six edge-sharing {VO5 N} octahedra incorporating six {(OCH2 CH2 )2 N(CH2 CH2 OH)} ligands. Two (OCH2 CH2 –) arms of each of the six triethanolamine ligands are directly incorporated into the oxometalate core and the third {–CH2 CH2 OH} 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, [VIV6O6 {(OCH2 CH2 )2 N(CH2 CH2 OH)}6 ], is the isopolyoxovanadium analogue to the cationic clusters contained in a series of heteropolyoxovanadium compounds previously introduced by our laboratory, e.g., [LiVIV6O6 {(OCH2 CH2 )2 N(CH2 CH2 OH)}6 ] + ; its existence shows that a heteroatom is not required to form or stabilize the common organofunctionalized vanadium oxide framework: [VIV6O6 {(OCH2 CH2 )2 N(CH2 CH2 OH)}6 ]. 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.