RESUMO
The results reported here represent the first direct experimental observations supporting the existence of a solid-to-solid phase transition induced by thermal treatment in magnetic ionic liquids (MILs). The phase transitions of the solid phases of 1,3-dimethylimidazolium tetrachloroferrate, DimimFeCl4, are closely related to its thermal history. Two series of solid-to-solid phase transitions can be described in this MIL: (i) from room temperature (RT) phase II [space group (s.g.) = P21] to phase I-a [s.g. = P212121] via thermal quenching or via fast cooling at T > 2 K min(-1); (ii) from phase I-a to phase I-b [s.g. = P21/c] when the temperature was kept above 180 K for several minutes. The latter involves a slow translational and reorientational dynamical process of both the imidazolium cation and the tetrachloroferrate anion and has been characterized using synchrotron and neutron powder diffraction and DFT (density functional theory) studies. The transition is also related to the modification of the super-exchange pathways of low-temperature phases which show a overall antiferromagnetic behavior. A combination of several experimental methods such as magnetometry, Mössbauer and muon spectroscopy together with polarized and non-polarized neutron powder diffraction has been used in order to characterize the different features observed in these phases.
RESUMO
We present the first magnetic phase of an ionic liquid with anion-π interactions, which displays a three-dimensional (3D) magnetic ordering below the Néel temperature, TN = 7.7 K. In this material, called Dimim[FeBr4], an exhaustive and systematic study involving structural and physical characterization (synchrotron X-ray, neutron powder diffraction, direct current and alternating current magnetic susceptibility, magnetization, heat capacity, Raman and Mössbauer measurements) as well as first-principles analysis (density functional theory (DFT) simulation) was performed. The crystal structure, solved by Patterson-function direct methods, reveals a monoclinic phase (P21 symmetry) at room temperature with a = 6.745(3) Å, b = 14.364(3) Å, c = 6.759(3) Å, and ß = 90.80(2)°. Its framework, projected along the b direction, is characterized by layers of cations [Dimim](+) and anions [FeBr4](-) that change the orientation from layer to layer, with Fe···Fe distances larger than 6.7 Å. Magnetization measurements show the presence of 3D antiferromagnetic ordering below TN with the existence of a noticeable magneto-crystalline anisotropy. From low-temperature neutron diffraction data, it can be observed that the existence of antiferromagnetic order is originated by the antiparallel ordering of ferromagnetic layers of [FeBr4](-) metal complex along the b direction. The magnetic unit cell is the same as the chemical one, and the magnetic moments are aligned along the c direction. The DFT calculations reflect the fact that the spin density of the iron ions spreads over the bromine atoms. In addition, the projected density of states (PDOS) of the imidazolium with the bromines of a [FeBr4](-) metal complex confirms the existence of the anion-π interaction. Magneto-structural correlations give no evidence for direct iron-iron interactions, corroborating that the 3D magnetic ordering takes place via superexchange coupling, the Fe-Br···Br-Fe interplane interaction being defined as the main exchange pathway.
RESUMO
A new magnetic ionic liquid (MIL) with 3D antiferromagnetic ordering has been synthetized and characterized. The information obtained from magnetic characterization was supplemented by analysis of DFT calculations and the magneto-structural correlations. The result gives no evidence for direct iron-iron interactions, corroborating that the 3D magnetic ordering in MILs takes place via super-exchange coupling containing two diamagnetic atoms intermediaries.
RESUMO
We report a combined study using magnetization and Raman spectroscopy on the magnetic ionic liquid 1-ethyl-3-methylimidazolium tetrachloroferrate, Emim[FeCl4]. This material shows a long-range antiferromagnetic ordering below the Néel temperature T(N) ≈ 3.8 K. The effects of pressure on the magnetic properties have been studied using a miniature piston-cylinder CuBe pressure cell. This three-dimensional ordering is strongly influenced when hydrostatic pressure is applied. It is observed that low applied pressure is enough to modify the magnetic interactions, inducing a transition from antiferromagnetic to ferrimagnetic ordering. Raman spectroscopy measurements reveal important information about the existence of isolated [FeCl4](-) anions and the absence of dimeric [Fe2Cl7](-) units in the liquid and solid states. These features seem to suggest that the superexchange pathways responsible for the appearance of magnetic ordering are mediated through Fe-Cl-Cl-Fe. Furthermore, the liquid-solid phase transition exhibits a magnetic hysteresis near room temperature, which can be tuned by weak pressures.
