Solid state coordination chemistry of the oxofluorovanadium-diphosphonate system in the presence of Cu(II)-tetrapyridylpyrazine complex cations. The crystal structures of [{Cu2(tpyprz)(H2O)2}V4FO 8(HO3PCH2PO3)2], [{Cu2(tpyprz)(H2O)2}V4F 6O...

Wayne Ouellette, Vladimir Golub, Charles J. O'Connor, Jon Zubieta

Research output: Contribution to journalArticle

23 Scopus citations

Abstract

Full title: Solid state coordination chemistry of the oxofluorovanadium-diphosphonate system in the presence of Cu(II)-tetrapyridylpyrazine complex cations. The crystal structures of [{Cu2(tpyprz)(H2O)2}V4FO 8(HO3PCH2PO3)2], [{Cu2(tpyprz)(H2O)2}V4F 6O6(O3PCH2CH2PO 3)], and [Cu2(tpyprz){HO3P(CH2)3PO 3H}][V2F2O5] (tpyprz=tetra-4-pyridylpyrazine). The hydrothermal reactions of V2O5, Cu(CH3CO2)2·H2O, tetrapyridylpyrazine (tpyprz), HF and the appropriate diphosphonic acid yielded a series of compounds of the {Cu2 (tpyprz)} 4+ / Vx Oy Fzn - / {O3 P (CH2)n PO3} 4- family of materials. The structure of [{Cu2(tpyprz)(H2O)2}V4F 6O6(HO3PCH2PO3) 2] (1) is one-dimensional, constructed from mixed valence {V3V VIV FO8 (HO3 PCH2 PO3)2}4 - clusters linked through {Cu2(tpyprz)(H2O)2}4+ rods. The two-dimensional [{Cu2(tpyprz)(H2O)2}V4F 6O6(O3PCH2CH2PO 3)] (2) is constructed from {V4 F6 O6 (O3 PCH2 CH2 PO3)}n4 n - chains crosslinked by {Cu2(tpyprz))(H2O)2}4+ rods; mixed valence {V2V V2IV F6 O6 (O3 PCH2 CH2 PO3)}4 - clusters are embedded in the network. Compound 3, [Cu2(tpyprz){HO3P(CH2)3PO 3H}][V2F2O5], consists of [Cu2 (tpyprz) {HO3 P (CH2)3 PO3 H}]n2 n + chains and isolated {V2F2O5}2- anions. Structures 1-3 are compared to the structures of the analogous series {Cu2 (bisterpy)}4 + / Vx Oy Fzn - / {O3 P (CH2)n PO3}4 -, where bisterpy is 2,2′:4′:4″:2″,2‴-quaterpyridine, 6′,6″-di-2-pyridinyl. The temperature-dependent magnetic susceptibilities of 2 and 3 are also discussed.

Original languageEnglish (US)
Pages (from-to)2500-2509
Number of pages10
JournalJournal of Solid State Chemistry
Volume180
Issue number9
DOIs
StatePublished - Sep 1 2007

Keywords

  • Bimetallic oxides
  • Copper-tetrapyridylpyridine components
  • Organic-inorganic hybrid materials
  • Oxyfluorovanadates
  • Vanadium organophosphonates

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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