1-Ethyl-2,3-dimethylimidazolium paramagnetic ionic liquids with 3D magnetic ordering in its solid state: Synthesis, structure and magneto-structural correlations
60835 - 60848
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© The Royal Society of Chemistry 2015.Two novel paramagnetic ionic liquids, comprised of a 1-ethyl-2,3-dimethylimidazolium (Edimim) cation and a tetrahaloferrate(iii) (FeX<inf>4</inf>) (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[FeCl<inf>4</inf>] and Edimim[FeBr<inf>4</inf>] 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-π. Magnetization measurements show the presence of three-dimensional antiferromagnetic ordering below the Néel temperature (T<inf>N</inf>) 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[FeX<inf>4</inf>] (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 T<inf>N</inf>. In contrast, the comparative study with Dimim[FeX<inf>4</inf>] (X = Cl and Br) compounds (Dimim: 1,3-dimethylimidazolium) shows a lower T<inf>N</inf> in the chloride compound, Edimim[FeCl<inf>4</inf>], whereas it is higher for the bromide, Edimim[FeBr<inf>4</inf>]. This fact is attributed to the spin delocalization of iron atoms in [FeBr<inf>4</inf>]<sup>-</sup> 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.
AuthorsGarcía-Saiz, A; De Pedro, I; Vallcorba, O; Migowski, P; Hernández, I; Fernández Barquin, L; Abrahams, I; Motevalli, M; Dupont, J; Gonzalez, JA; Fernández, JR
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