Secondary metal-ligand cationic subunits {ML}n+ as structural determinants in the oxovanadium/phenylphosphonate/{ML}n+ system, where {ML} is a Cu2+/organonitrogen moiety

Gundog Yucesan, Hui Yu Ming, Wayne Ouellette, Charles J. O'Connor, Jon A Zubieta

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Abstract

The hydrothermal reactions of CuSO4·5H2O, Na3VO4, phenylphosphonic acid and the appropriate organonitrogen ligand yield a series of materials of the oxovanadium/ phenylphosphonate/Cu(II)-ligand family. The structural influences of the organonitrogen ligand are most pronounced in the dimensionality of the material. Thus, [{Cu(phen)}VO(O3PC6H5) 2]·0.5 H2O (1) is one-dimensional; [{Cu 2(bpytrz)(H2O)}VO(O3PC6H 5)2(HO3PC6H5)] (2) (bpytrz 5 3,5-di-2-pyridyl-1,2,4-triazolate) is two-dimensional, and [{Cu(4,4′-bpy)}0.5VO2(O3PC 6H5)] (3) is three-dimensional. When the phenylphosphonate component is replaced by phenyl-1,2-diphosphonate, the three-dimensional material [{Cu(4,4′-bpy)}VO2(HO3PC6H 4PO3)] (4) is obtained. In contrast to the structure of 3 which exhibits a three-dimensional Cu-V-P-O substructure which encapsulates the {Cu2(bpy)}4+ unit, 4 exhibits the more common "pillared" layer structure with Cu-V-P-O networks buttressed by the 4,4′-bipyridyl groups. When the starting materials that gave 4 are reacted at 200°C rather than 120°C, the copper phase [{Cu(4,4′-bpy) 0.5}{Cu(H2O)}(O3PC6H 4PO3)]·H2O (5) is obtained. Compound 5 exhibits a "pillared" layer structure with a Cu-P-O network exhibiting embedded binuclear copper(II) sites.

Original languageEnglish (US)
Pages (from-to)480-490
Number of pages11
JournalCrystEngComm
Volume7
DOIs
StatePublished - Jul 19 2005

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ASJC Scopus subject areas

  • Condensed Matter Physics

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