Solid state coordination chemistry of the oxovanadium-diphosphonate system: Structural consequences of aryl tethers on materials of the type cation/VxOy/diphos, where cation = organoammonium and diphos = 1,4-phenyldiphosphonic acid |
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Authors: | Paul DeBurgomaster Wayne Ouellette Jon Zubieta |
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Institution: | a Department of Chemistry, Syracuse University, Syracuse, NY 13244, United States b Advanced Materials Institute, University of New Orleans, New Orleans, LA 70148, United States |
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Abstract: | Hydrothermal reactions of V2O5, 1,4-phenyldiphosphonic acid and an appropriate organoamine, in the presence of HF as solubilizer, were exploited to prepare a series of materials of the general type organoammonium cation]nVxOy(HmO3PC6H4PO3Hp)3]. Compound 1, H3N(CH2)4NH3]V2O4(O3PC6H4PO3)], exhibits a one-dimensional V-P-O substructure, linked through the phenyl tethers of the ligand into a layer. Compound 1 is a unique example of a V(V)-diphosphonate phase. Compounds 2 and 3, H3N(CH2)2NH3]V2O2(O3PC6H4PO3H)2] and H2pip]V2O2(O3PC6H4PO3H)2] (H2pip = piperazinium), exhibit identical two dimensional substructures, constructed from ribbons connected through the phenyl tethers of the ligands. The three-dimensional framework of H3N(CH2)7NH3]2V3O4(O3PC6H4PO3)2] (4) consists of V-P-O layers characterized by trinuclear V(IV)-oxide subunits and 9 and 12 polyhedral connect rings; the layers are buttressed by the phenyl spacers to provide the typical “pillared” layer structure common to metal diphosphonate materials. Compound 5, H2dabco]V2F3O2(O3PC6H4PO3H)]·H2O, is also three-dimensional with oxyfluoro-vanadium(IV) chains linked through the diphosphonate ligands into a framework structure with void spacers to accommodate the {H2dabco}2+ cations (dabco = diamino bicyclo octane). The magnetic properties of 2-5 reflect the structural characteristics of the materials. |
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Keywords: | Metal-diphosphonate compounds Oxovanadium-phosphonates Oxyfluoro-vanadates Hydrothermal synthesis Crystal structures |
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