Structural influences of organonitrogen ligands on vanadium oxide solids. Hydrothermal syntheses and structures of the terpyridine vanadates [V2O4(terpy)2]3[V10O28], [VO2(terpy)][V4O10], and [V9O22(terpy)3]

Pamela J. Hagrman, Jon Zubieta

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Abstract

Hydrothermal reactions of the V2O5/2,2':6':2''-terpyridine/ZnO/H2O system under a variety of conditions yielded the organic-inorganic hybrid materials [V2O4(terpy)2]3[V10O28]·2H2O (VOXI-10), [VO2(terpy)][V4O10] (VOXI-11), and [V9O22(terpy)3] (VOXI-12). The structure of VOXI-10 consists of discrete binuclear cations [V2O4-(terpy)2]2+ and one-dimensional chains [V10O28]6-, constructed of cyclic [V4O12]4- clusters linked through {VO4} tetrahedra. In contrast, the structure of VOXI-11 exhibits discrete mononuclear cations [VO2(terpy)]1+ and a two-dimensional vanadium oxide network, [V4O10]1-. The structure of the oxide layer is constructed from ribbons of edge-sharing square pyramids; adjacent ribbons are connected through comer-sharing interactions into the two-dimensional architecture. VOXI-12 is also a network structure; however, in this case the terpy ligand is incorporated into the two-dimensional oxide network whose unique structure is constructed from cyclic [V6O18]6- clusters and linear {V3O5(terpy)3} moieties of corner-sharing vanadium octahedra. The rings form chains through comer-sharing linkages; adjacent chains are connected through the trinuclear units. Crystal data: VOXI-10, C90H70N18O42V16, triclinic P1, a = 12.2071(7) Å, b = 13.8855(8) Å, 16.9832(10) Å, α = 69.584(1)°, β = 71.204(1)°, γ = 84.640(1)°, Z = 1; VOXI-11, C15H11N3O12V5, monoclinic, P21/n, a = 7.7771(1) Å, b = 10.3595(2) Å, c = 25.715(4) Å, β = 92.286(1)°, Z = 4; VOXI-12, C45H33N9O22V9, monoclinic C2/c, a = 23.774(2) Å, b = 9.4309(6) Å, c = 25.380(2) Å, β = 112.047(1)°, Z = 4.

Original languageEnglish (US)
Pages (from-to)3252-3260
Number of pages9
JournalInorganic Chemistry
Volume39
Issue number15
DOIs
StatePublished - Jul 24 2000

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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