Solid state coordination chemistry of the oxofluorovanadium-diphosphonate system in the presence of Cu(II)-tetrapyridylpyrazine complex cations

Journal Article · Sat Sep 15 04:00:00 EDT 2007 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2007.06.020· OSTI ID:21043834

Ouellette, Wayne ^[1]; Golub, Vladimir; O'Connor, Charles J ^[2]; Zubieta, Jon ^[1]

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1. Department of Chemistry, Syracuse University, Syracuse, NY 13244-4100 (United States)
2. Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148 (United States)

The hydrothermal reactions of V{sub 2}O{sub 5}, Cu(CH{sub 3}CO{sub 2}){sub 2}.H{sub 2}O, tetrapyridylpyrazine (tpyprz), HF and the appropriate diphosphonic acid yielded a series of compounds of the {l_brace}Cu{sup 2}(tpyprz){r_brace}{sup 4+}/V{sub x}O{sub y}F{sub z}{sup n-}/{l_brace}O{sub 3}P(CH{sub 2}){sub n}PO{sub 3}{r_brace}{sup 4-} family of materials. The structure of [{l_brace}Cu{sub 2}(tpyprz)(H{sub 2}O){sub 2}{r_brace}V{sub 4}F{sub 6}O{sub 6}(HO{sub 3}PCH{sub 2}PO{sub 3}){sub 2}] (1) is one-dimensional, constructed from mixed valence {l_brace}V{sub 3}{sup V}V{sup IV}FO{sub 8}(HO{sub 3}PCH{sub 2}PO{sub 3}){sub 2}{r_brace}{sup 4-} clusters linked through {l_brace}Cu{sub 2}(tpyprz)(H{sub 2}O){sub 2}{r_brace}{sup 4+} rods. The two-dimensional [{l_brace}Cu{sub 2}(tpyprz)(H{sub 2}O){sub 2}{r_brace}V{sub 4}F{sub 6}O{sub 6}(O{sub 3}PCH{sub 2}CH{sub 2}PO{sub 3})] (2) is constructed from {l_brace}V{sub 4}F{sub 6}O{sub 6}(O{sub 3}PCH{sub 2}CH{sub 2}PO{sub 3}){r_brace}{sub n}{sup 4n-} chains crosslinked by {l_brace}Cu{sub 2}(tpyprz))(H{sub 2}O){sub 2}{r_brace}{sup 4+} rods; mixed valence {l_brace}V{sub 2}{sup V}V{sub 2}{sup IV}F{sub 6}O{sub 6}(O{sub 3}PCH{sub 2}CH{sub 2}PO{sub 3}){r_brace}{sup 4-} clusters are embedded in the network. Compound 3, [Cu{sub 2}(tpyprz){l_brace}HO{sub 3}P(CH{sub 2}){sub 3}PO{sub 3}H{r_brace}][V{sub 2}F{sub 2}O{sub 5}], consists of [Cu{sub 2}(tpyprz){l_brace}HO{sub 3}P(CH{sub 2}){sub 3}PO{sub 3}H{r_brace}]{sub n}{sup 2n+} chains and isolated {l_brace}V{sub 2}F{sub 2}O{sub 5}{r_brace}{sup 2-} anions. Structures 1-3 are compared to the structures of the analogous series {l_brace}Cu{sub 2}(bisterpy){r_brace}{sup 4+}/V{sub x}O{sub y}F{sub z}{sup n-}/{l_brace}O{sub 3}P(CH{sub 2}){sub n}PO{sub 3}{r_brace}{sup 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. - Graphical abstract: Hydrothermal reactions have been exploited in the preparation of a series of bimetallic oxides constructed from {l_brace}Cu{sub 2}(tpyprz){r_brace}{sup 4+} and oxyfluorovanadium organophosphonate components. A view of the two-dimensional structure of the mixed valence [{l_brace}Cu{sub 2}(tpyprz)(H{sub 2}O){sub 2}{r_brace}V{sub 4}F{sub 6}O{sub 6}(O{sub 3}PCH{sub 2}CH{sub 2}PO{sub 3})] is provided.

• OSTI ID: 21043834
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 9 Vol. 180; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
COORDINATION NUMBER
COORDINATION VALENCES
COPPER COMPLEXES
CROSS-LINKING
HYDROFLUORIC ACID
MAGNETIC SUSCEPTIBILITY
OXYFLUORIDES
PHOSPHONATES
PHOSPHONIC ACIDS
TEMPERATURE DEPENDENCE
VANADIUM COMPOUNDS
VANADIUM OXIDES