Hydrothermal Synthesis and Structural Characterization of V(III)-Containing Phases of the Vanadium Organodiphosphonate System. Crystal Structures of the V(III) Species (H30)[V3(03PCH2CH2P03)(H03PCH2CH2P03H)3] and of the Mixed Valence V(III)/V(IV) Material (H30)2[(V0)V2(0H)2(03PCH2CH2P03)2]H20

Victoria Soghomonian, Robert C. Haushalter, Jon Zubieta

Research output: Contribution to journalArticle

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Abstract

The recent expansion of the chemistry of metal organophosphonate materials reflects their practical applications as sorbents, ion exchangers, catalysts, and hosts in intercalation compounds. Furthermore, the organophosphonate building blocks may be modified so as to allow the targeted design of solid-phase materials. The vanadium organophosphonate system provides a particularly rich structural chemistry which may be extended by exploiting linked diphosphonate groups with tethers of varying length or structure. Under reducing conditions, the introduction of octahedral V(III) sites into the mix of structural motifs further diversifies the structural chemistry of the system. In a typical preparation, the reaction of a mixture of VC14, H2O3PCH2CH2PO3H2, H2NC2H4NH2, and H20 in the mole ratio 1:3.11:5.10:1890 at 200 °C for 87 h produced bright green truncated cubes of (H30)[V3(03PCH2CH2P03)(H03- PCH2CH2PO3H)3] (1) and blue green plates of (H3O)2[(VO)V2(OH)2(O3PCH2CH2PO3)2].H2O (2) in yields of 5% and 45%, respectively. The structure of 1 consists of layers of comersharing vanadium(III) octahedra {VO6} and phosphorus tetrahedra, pillared by the organic backbone of the ethylenediphosphonate groups. The polyhedral connectivity pattern results in the formation within the layers of cavities defined by the corner-sharing of six vanadium octahedra and six phosphorus tetrahedra and occupied by the hydronium cations. While the framework of 2 is similarly composed of V-P-0 layers buttressed by the organic backbones of the ethylenediphosphonate groups, the layer structure is distinct from that of 1. Compound 2 exhibits polyhedral connectivity resulting from the corner-sharing the V(III) octahedra, V(IV) square pyramids, and phosphorus tetrahedra which defines cavities constructed from four V(III), two V(IV), and four phosphorus polyhedral. Crystal data: 1: R3c, a = 9.863(1), c = 46.403(9), V = 3090(2) Å3, Z = 6, Dcalc = 2.346 g/cm3; structure refinement and solution based on 597 reflections (Mo Kα, λ = 0.710 73 Å) converged at R = 0.0763. 2: PI, a = 7.150(1), b 7.809(2) Å, c = 9.996(2) Å, a = 76.55(2)°, β = 70.17(2)°, γ = 88.91(2)°, V = 509.5(3) Å3, Z = 1, Dcalc = 2.056 g/cm3; 1281 reflections, R = 0.0740.

Original languageEnglish (US)
Pages (from-to)1648-1654
Number of pages7
JournalChemistry of Materials
Volume7
Issue number9
DOIs
StatePublished - Sep 1995

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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