Synthesis, structure determination and magnetic behaviour of the first porous hybrid oxyfluorinated vanado(III)carboxylate: MIL-71 or VIII2(OH)2F2{O2C-C6H4-CO2}·H2O

K. Barthelet; K. Adil; F. Millange; C. Serre; D. Riou; G. Férey

doi:10.1039/B306852H

Synthesis, structure determination and magnetic behaviour of the first porous hybrid oxyfluorinated vanado(iii)carboxylate: MIL-71 or Vⁱⁱⁱ₂(OH)₂F₂{O₂C-C₆H₄-CO₂}·H₂O

K. Barthelet,^a K. Adil,^a F. Millange,^a C. Serre,^a D. Riou^a and G. Férey*^a

* Corresponding authors

^a Institut Lavoisier-Franklin, UMR CNRS 8637, Université de Versailles St Quentin en Yvelines, 45 Av. des Etats-Unis, Versailles Cedex, France
E-mail: ferey@chimie.uvsq.fr
Fax: (33) 1 39 25 43 58
Tel: (33) 1 39 25 43 71

Abstract

A new type of three-dimensional vanadium(III) dicarboxylate, MIL-71 or V^III₂(OH)₂F₂{O₂C-C₆H₄-CO₂}·H₂O, has been obtained under hydrothermal conditions from aqueous mixtures of vanadium, 1,4-benzenedicarboxylic acid, and HF. MIL-71cal or V^IV₂O₂F₂{O₂C-C₆H₄-CO₂} is obtained by calcination of the parent compound in air at 250 °C. The three-dimensional structure of MIL-71 (S.G.: Cmmm; a = 21.4477(8) Å, b = 7.1449(2) Å, c = 3.8246(2) Å, and Z = 2) consists of layers built from corner-sharing {V^IIIO₂(OH)₂F₂} octahedra connected by the terephthalate linkers. The role of fluorine in this structure is understood by comparison with the already known hybrid vanado(III)carboxylates. The thermal behavior of the two solids has been investigated using TGA and X-ray thermodiffractometry. Finally, magnetic measurements performed on both MIL-71 and MIL-71cal reveal a canted antiferromagnetic behavior with Néel temperatures below 20 K.

Article information

https://doi.org/10.1039/B306852H

Article type

Paper

Submitted

16 Jun 2003

Accepted

17 Jul 2003

First published

30 Jul 2003

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J. Mater. Chem., 2003,13, 2208-2212

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Synthesis, structure determination and magnetic behaviour of the first porous hybrid oxyfluorinated vanado(III)carboxylate: MIL-71 or V^III₂(OH)₂F₂{O₂C-C₆H₄-CO₂}·H₂O

K. Barthelet, K. Adil, F. Millange, C. Serre, D. Riou and G. Férey, J. Mater. Chem., 2003, 13, 2208 DOI: 10.1039/B306852H

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Journal of Materials Chemistry