On the new low-dimensional organic–inorganic hybrid solids Cu4(bipy)4[V4P2O19]·nH2O (n				∼ 5) and Cu2(bipy)2[V2P2O12] with linear [V4P2O19]8− and cyclic [V2P2O12]4− oligomers

S. Ushak; E. Spodine; D. Venegas-Yazigi; E. Le Fur; J. Y. Pivan; O. Peña; R. Cardoso-Gil; R. Kniep

doi:10.1039/B508928J

On the new low-dimensional organic–inorganic hybrid solids Cu₄(bipy)₄[V₄P₂O₁₉]·nH₂O (n ∼ 5) and Cu₂(bipy)₂[V₂P₂O₁₂] with linear [V₄P₂O₁₉]⁸⁻ and cyclic [V₂P₂O₁₂]⁴⁻ oligomers†

S. Ushak,^a E. Spodine,*^a D. Venegas-Yazigi,^a E. Le Fur,*^b J. Y. Pivan,^b O. Peña,^b R. Cardoso-Gil^c and R. Kniep*^c

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* Corresponding authors

^a Centro para la Investigacion Interdisciplinaria Avanzada en Ciencia de los Materiales (CIMAT), Facultad de Ciencias Quimicas y Farmaceuticas, Universidad de Chile, Casilla 233, Santiago, Chile
E-mail: espodine@uchile.cl
Fax: (+56) 2 6782868
Tel: (+56) 2 6782862

^b Laboratoire de Chimie du Solide et Inorganique Moléculaire, UMR 6511 CNRS-Université de Rennes 1-ENSCR, Institut de Chimie de Rennes, 35042 Rennes Cedex, France
E-mail: eric.le-fur@ensc-rennes.fr
Fax: (+33) 223 238 199
Tel: (+33) 223 238 016

^c Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Straße 40, 01187 Dresden, Germany
E-mail: kniep@cpfs.mpg.de
Fax: (+49) 351 4646 3002
Tel: (+49) 351 4646 3001

Abstract

The new hybrid organic–inorganic copper oxovanadium phosphates of composition Cu₄(bipy)₄V₄O₁₁(PO₄)₂·nH₂O (n ∼ 5) (1) and Cu₂(bipy)₂V₂P₂O₁₂ (2) (bipy = 2, 2′-bipyridine) adopting the triclinic symmetry were obtained by soft hydrothermal routes. Both structures present different oxovanadium phosphate anionic units, resulting from the vertex-sharing of PO₄ and VO₄ tetrahedra, which are coordinated to copper diimine cationic groups to form a 1D framework. The VPO structures are reminiscent of the known connectivity and geometry of polyphosphate anions. For the two compounds, the magnetic copper(II) centres are square pyramidally coordinated with two nitrogen atoms of the neutral diimine ligand and three oxygen atoms of the oxovanadium phosphate subunit. The CuN₂O₃ pyramids are linked together by oxo-bridges involving PO₄ tetrahedra in Cu₂(bipy)₂V₂P₂O₁₂ with the closest Cu–Cu distances corresponding to 4.98 Å. Edge-sharing of the copper pyramids in Cu₄(bipy)₄V₄O₁₁(PO₄)₂·nH₂O results in the binuclear unit {Cu₂O₄N₄}, with Cu–Cu distances of 3.19 Å. Additional links of these dimers by phosphate oxo-bridges result in the formation of rectangular tetramers Cu₄ with a copper–copper separation of approximately 4.10 Å. Results of thermal analysis and magnetic susceptibility are presented.

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DOI: https://doi.org/10.1039/B508928J
Article type: Paper
Submitted: 23 Jun 2005
Accepted: 08 Aug 2005
First published: 12 Sep 2005

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J. Mater. Chem., 2005,15, 4529-4534

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On the new low-dimensional organic–inorganic hybrid solids Cu₄(bipy)₄[V₄P₂O₁₉]·nH₂O (n ∼ 5) and Cu₂(bipy)₂[V₂P₂O₁₂] with linear [V₄P₂O₁₉]⁸⁻ and cyclic [V₂P₂O₁₂]⁴⁻ oligomers

S. Ushak, E. Spodine, D. Venegas-Yazigi, E. L. Fur, J. Y. Pivan, O. Peña, R. Cardoso-Gil and R. Kniep, J. Mater. Chem., 2005, 15, 4529 DOI: 10.1039/B508928J

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Journal of Materials Chemistry