1-Ethyl-2,3-dimethylimidazolium paramagnetic ionic liquids with 3D magnetic ordering in its solid state: synthesis, structure and magneto-structural correlations

Abstract: Two novel paramagnetic ionic liquids, comprised of a 1-ethyl-2,3-dimethylimidazolium (Edimim) cation and a tetrahaloferrate(III) (FeX4) (X = Cl and Br) anion were synthetized and characterized by thermal, structural, Raman spectroscopy and magnetic studies. The crystal structures, determined by synchrotron X-ray powder diffraction and single crystal X-ray diffraction at 100 K for Edimim[FeCl4] and Edimim[FeBr4] respectively, are characterized by layers of cations (in non-planar configuration) and anions stacked upon one another in a three-dimensional (3D) manner with several non-covalent interactions: halide–halide, hydrogen bond and anion–p. Magnetization measurements show the presence of three-dimensional antiferromagnetic ordering below the Néel temperature (TN) with the existence of a noticeable magneto-crystalline anisotropy in the bromide compound. The corresponding magneto-structural correlations evidence that the 3D magnetic ordering mainly takes place via Fe–X?X–Fe (X = Cl and Br) interactions, displaying a higher superexchange magnetic interaction between the planes. Comparison with the Emim[FeX4] (X = Cl and Br) phases (Emim: 1-ethyl-3-methylimidazolium) reveals that the methylation at the C(2) position onto the imidazolium cation ring causes an increase of the melting point and a decrease of the TN. In contrast, the comparative study with Dimim[FeX4] (X = Cl and Br) compounds (Dimim: 1,3-dimethylimidazolium) shows a lower TN in the chloride compound, Edimim[FeCl4], whereas it is higher for the bromide, Edimim[FeBr4]. This fact is attributed to the spin delocalization of iron atoms in [FeBr4]- and discards the hypothesis that a bigger imidazolium ion size causes a weaker magnetic coupling in paramagnetic ionic liquids based on tetrahaloferrate anions and imidazolium cations with 3D magnetic ordering in its solid state.

 Autoría: García-Saiz A., De Pedro I., Vallcorba O., Migowski P., Hernández I., Fernández Barquin L., Abrahams I., Motevalli M., Dupont J., Gonzalez J., Fernández J.,

 Fuente: RSC Advances, 2015, 75, (5), 60835-60848

Editorial: Royal Society of Chemistry

 Año de publicación: 2015

Nº de páginas: 14

Tipo de publicación: Artículo de Revista

DOI: 10.1039/C5RA05723J

ISSN: 2046-2069

Proyecto español: MAT2011-27573-C04

Url de la publicación: https://doi.org/10.1039/C5RA05723J