Hydrothermal chemistry of vanadium oxides with aromatic di- and tri-phosphonates in the presence of secondary metal copper(II) cationic complex subunits

Paul Deburgomaster, Wayne Ouellette, Hongxue Liu, Charles J. O'Connor, Jon Zubieta

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Abstract

The hydrothermal chemistry of the copper-organonitrogen ligand/vanadium oxide/aromatic phosphonate system has been studied. Not only was HF required to induce crystallization, but product composition was highly dependent on the HF/V ratio of the reactions. At relatively low concentrations of HF/V of 6:1, materials of the Cu(II)-ligand/VxOy/organophosphonate type were observed, namely, [{Cu(phen)}2V2O5(O 3PC6H4PO3)] (1), [Cu(phen)VO 2(HO3PC6H4PO3)] (2), [{Cu(terpy)}2V2O5(O3PC 6H4PO3)] (3), [{Cu(phen)(H2O)} VO2(HO3PC6H4PO3)] (6), [{Cu(phen)}VO2(HO3PC6H4PO 3)] (7a and 7b), [Cu(C5H4NCO2) 2V2O4(HO3PC6H 4POH3)] (8), [Cu(bpy)VO2 {(HO 3P)3C6H3}]·1.5H2O (12·1.5H2O), [{Cu(bpy)}2V3O 7{(O3P)2C6H3PO 3H}] (13) and [Cu(phen)V3O6(H 2O){(O3P)2C6H3(PO 3H)}] (14). When the HF concentration was raised, materials incorporating fluoride anion were observed; that is, compounds of the Cu(II)-ligand/VxOyFz/organophosphonate type: [{Cu(bpa)}2VO2F(H2O)(O3PC 6H4PO3)]·H2O (4), [{Cu(bpa)}2V2O4F2(O 3PC6H4PO3)] (5), [{Cu(bpy)} 2V2O4F2(O3PC 6H4PO3)] (9), [{Cu(terpy)}2V 3O6F(HO3PC6H4PO 3)2] (10), [{Cu(bpa)}2V2O 4F2(O3PC6H4PO 3)] (11). At HF/V concentrations of 25:1 or greater, vanadium free products, Cu(II) ligand/organophosphonate, were obtained: [Cu(C 5H4NCO2)2(H2O 3PC6H4PO3H2)] ·H2O (15·H2O), [Cu(C5H 4NCO2)2(H2O3PC 6H4PO3H2)] (16), [Cu(bpy)(H 2O){(HO3P)2C6H3(PO 3H2)}] (17), [Cu(bpy){(HO3P)2C 6H3(PO3H2)}]·H2O (18·H2O), [Cu(phen){(H2O3P)C 6H3(PO3H)2}]·2H2O (19·2H2O) and [Cu(bpa){H2O3PC 6H3(PO3H)2}]·H2O (20·H2O). The structural chemistry is unusually diverse with the Cu(II) ligand/VxOy/organophosphonate series exhibiting one-, two- and three-dimensional structures with a variety of copper-vanadate and vanadophosphonate substructures. The structural chemistry is discussed in relation to other examples of materials of the Cu(II) ligand/VxO y/organophosphonate and Cu(II) ligand/VxO yFz/organophosphonate families.

Original languageEnglish (US)
Pages (from-to)446-469
Number of pages24
JournalCrystEngComm
Volume12
Issue number2
DOIs
StatePublished - Apr 6 2010

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ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

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