Solid-state coordination chemistry: Structural influences of copper-phenanthroline subunits on oxovanadium organophosphonate phases. Hydrothermal synthesis and structural characterization of the two-dimensional materials [Cu(phen)(VO)(O3PCH2PO3)(H2O)]

R. C. Finn, R. Lam, J. E. Greedan, J. Zubieta

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Abstract

The hydrothermal reactions of CuCl2·2H2O, Na3VO4, 1,10-phenanthroline, and the appropriate organodiphosphonate ligand yield [Cu(phen)(VO)(O3PCH2PO3)(H2O)] (1), [{Cu(phen)}2(V2O5) (O3PCH2CH2PO3)] (2), [{Cu(phen)}2(V3O5) (O3PCH2CH2CH2 PO3)2 (H2O)] (3), and [{Cu(phen)}2(V3O5) (O3PCH2PO3)2(H2O)] (4). Compounds 1-3 exhibit two-dimensional structures. The structures exhibit distinct vanadium building blocks: square pyramidal, mononuclear V(IV) sites in 1, a binuclear unit of corner-sharing V(V) tetrahedra in 2, and a trinuclear unit of corner-sharing V(V) square pyramids and a V(IV) octahedron in 3. The network structures of 1 and 2 are constructed from one-dimensional oxovanadium-diphosphonate chains linked by Cu(II) square pyramids into two-dimensional layers. In contrast, compound 3 exhibits a two-dimensional oxovanadium-organodiphosphonate network, with Cu(II) sites decorating the surfaces. Compound 4 is unique in exhibiting a framework structure, which may be described as a three-dimensional oxovanadium-organodiphosphonate substructure with {Cu(phen)}2+ subunits covalently attached to the surface of channels running parallel to the a-axis. The magnetic properties of 1-4 are also correlated to the structural characteristics. The magnetic behavior of 2 is thus dominated by antiferromagnetic interactions. The magnetic behavior of 1 and 4 is consistent with the presence of two distinct paramagnetic metal ions, Cu(II) and V(IV). In contrast, 3 does not exhibit ferrimagnetic behavior, but rather weak antiferromagnetic coupling. Crystal data: 1, C13H10N2CuP2VO8, monoclinic P21/c, a = 9.0656(5) Å, b = 8.6584(5) Å, c = 20.934(1) Å, β = 97.306(1)°, Z = 4; 2, C26H20N4Cu2 P2V2O11, triclinic P1, a = 10.6096(5) Å, b = 11.6951(5) Å, c = 13.1796(6) Å, α = 71.369(1)°, β= 70.790(1)°, γ = 80.738(1)°, Z = 2; 3, C30H28N4Cu2 P4V3O18, triclinic P1, α = 9.4356(6) Å, b = 10.6556(6) Å, c = 11.0354(7) Å, α = 118.187(1)°, β= 91.416(1)°, γ = 107.821(1)°, Z = 1; 4, C26H20N4 Cu2P4V3O18, monoclinic, P21/c a = 8.3947(3) Å, b = 16.8401(7) Å, c = 11.9144(5) Å, β = 93.903(1)°, Z = 2.

Original languageEnglish (US)
Pages (from-to)3745-3754
Number of pages10
JournalInorganic Chemistry
Volume40
Issue number15
DOIs
StatePublished - Jul 16 2001

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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