Solid state coordination chemistry of the oxovanadium-diphosphonate system: Structural consequences of aryl tethers on materials of the type cation/V xOy/diphos, where cation = organoammonium and diphos = 1,4-phenyldiphosphonic acid

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

Research output: Contribution to journalArticle

7 Scopus citations

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]n[VxOy(H mO3PC6H4PO3H p)3]. Compound 1, [H3N(CH2) 4NH3][V2O4(O3PC 6H4PO3)], exhibits a one-dimensional V-P-O substructure, linked through the phenyl tethers of the ligand into a {V2O4(O3PC6H4PO3)}n2n- layer. Compound 1 is a unique example of a V(V)-diphosphonate phase. Compounds 2 and 3, [H3N(CH 2)2NH3][V2O2(O 3PC6H4PO3H)2] and [H 2pip][V2O2(O3PC6H 4PO3H)2] (H2pip = piperazinium), exhibit identical two dimensional {V2O2(O3PC6H4PO3H)2}n2n- substructures, constructed from {V2O2(O3PR)2(HO3PR)2}n2n- ribbons connected through the phenyl tethers of the ligands. The three-dimensional framework of [H 3N(CH2)7NH3]2[V 3O4(O3PC6H4PO 3)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(O 3PC6H4PO3H)]·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.

Original languageEnglish (US)
Pages (from-to)4065-4073
Number of pages9
JournalInorganica Chimica Acta
Volume363
Issue number14
DOIs
StatePublished - Nov 25 2010

Keywords

  • Crystal structures
  • Hydrothermal synthesis
  • Metal-diphosphonate compounds
  • Oxovanadium-phosphonates
  • Oxyfluoro-vanadates

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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