期刊
RSC ADVANCES
卷 5, 期 75, 页码 60835-60848出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5ra05723j
关键词
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资金
- Spanish Ministerio de Ciencia e Innovacion [MAT2011-27573-C04]
- Becas Iberoamericas Jovenes Profesores Investigadores, Santander Universidades
- EU [Marie Curie-CIG 303535]
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-pi. Magnetization measurements show the presence of three-dimensional antiferromagnetic ordering below the Neel temperature (T-N) 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 center dot center dot center dot 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.
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