Visible and Near-Infrared Emission by Samarium(III)-Containing Ionic Liquid Mixtures

Highly luminescent anionic samarium(III) beta-diketonate and dipicolinate complexes were dissolved in the imidazolium ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(6)mim][Tf2N]. The solubility of the complexes in the ionic liquid was ensured by a careful choice of the countercation of the samarium(III) complex. The samarium(III) complexes that were considered are [C(6)mim][SM(tta)(4)], where tta is 2-thenoyltrifluoroacetonate; [C(6)mim][Sm(nta)(4)], where nta is 2-naphthoyltrifluoroacetonate; [C(6)mim][Sm(hfa)(4)], where hfa is hexafluoroacetylacetonate; and [choline](3)-[Sm(dpa)(3)], where dpa is pyridine-2,6-dicarboxylate (dipicolinate) and [choline](+) is (2-hydroxyethyl)trimethyl ammonium. The crystal structures of the tetrakis samarium(III) P-diketonate complexes revealed a distorted square antiprismatic coordination for the samarium(III) ion in all three cases. Luminescence spectra were recorded for the samarium(III) complexes dissolved in the imidazolium ionic liquid as well as in a conventional solvent, that is, acetonitrile or water for the beta-diketonate and dipicolinate complexes, respectively. These experiments demonstrate that [C(6)mim][Tf2N] is a suitable spectroscopic solvent for studying samarium(III) luminescence. High-luminescence quantum yields were observed for the samarium(III) beta-diketonate complexes in solution.

Liquid-liquid equilibria of ternary 2M1B/2M2B-2M1BOH-H2O and quaternary 2M1B-2M2B-2M1BOH-H2O mixtures

Liquid-liquid equilibria of two ternary mixtures 2M1B-2M1BOH-H[2]O] and 2M2B-2M1BOH-H[2]O were measured at 5, 15 and 25 C. UNIQUAC and NRTL models were fitted to the experimental data using ASPEN PLUS. Both experimental and correlated values of equilibrium compositions were compared with the values predicted by UNIFAC method. The same procedure was extended to the quaternary mixture 2M1B-2M2B-2M 1BOH-H[2]O. The regressed results were in good agreements with experimental data. Original UNIFAC model performed better representation than Dortmund UNIFAC model.

Density-viscosity product of small-volume ionic liquid samples using quartz crystal impedance analysis

Quartz crystal impedance analysis has been developed as a technique to assess whether room-temperature ionic liquids are Newtonian fluids and as a small-volume method for determining the values of their viscosity-density product, rho eta. Changes in the impedance spectrum of a 5-MHz fundamental frequency quartz crystal induced by a water-miscible room-temperature ionic liquid, 1-butyl-3-methylimidazolium. trifluoromethylsulfonate ([C(4)mim][OTf]), were measured. From coupled frequency shift and bandwidth changes as the concentration was varied from 0 to 100% ionic liquid, it was determined that this liquid provided a Newtonian response. A second water-immiscible ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C(4)mim][NTf2], with concentration varied using methanol, was tested and also found to provide a Newtonian response. In both cases, the values of the square root of the viscosity-density product deduced from the small-volume quartz crystal technique were consistent with those measured using a viscometer and density meter. The third harmonic of the crystal was found to provide the closest agreement between the two measurement methods; the pure ionic liquids had the largest difference of similar to 10%. In addition, 18 pure ionic liquids were tested, and for 11 of these, good-quality frequency shift and bandwidth data were obtained; these 12 all had a Newtonian response. The frequency shift of the third harmonic was found to vary linearly with square root of viscosity-density product of the pure ionic liquids up to a value of root(rho eta) approximate to 18 kg m(-2) s(-1/2), but with a slope 10% smaller than that predicted by the Kanazawa and Gordon equation. It is envisaged that the quartz crystal technique could be used in a high-throughput microfluidic system for characterizing ionic liquids.

Crystal and liquid crystalline polymorphism in 1-alkyl-3-methylimidazolium tetrachloropalladate(II) salts

1-Alkyl-3-methylimidazolium tetrachloropalladate(ii) salts ([C-n-mim](2)[PdCl4], n = 10, 12, 14, 16, 18) containing a single, linear alkyl-chain substituent on the cation have been synthesised and their behaviour characterised by differential scanning calorimetry, polarising optical microscopy and small-angle X-ray scattering. The salts display thermotropic polymorphism, exhibiting both crystal-crystal transitions and, for n = 14-18, the formation of a thermotropic smectic liquid crystalline phase.

Estimation of ternary liquid-liquid equilibria for arene/alkane/ionic liquid mixtures using neural networks

Neural network models have been explored for the prediction of the liquid-liquid equilibrium data and aromatic/aliphatic selectivity values. Four ternary systems composed of toluene, heptane, and the ionic liquids 1-ethyl-3-methylimidazolium ethylsulfate, or 1,3-dimethylimidazolium methylsulfate were investigated at 313.2 and 348.2 K.

Temperature-Driven Mixing-Demixing Behavior of Binary Mixtures of the Ionic Liquid Choline Bis(trifluoromethylsulfonyl)imide and Water

The ionic liquid (2-hydroxyethylammonium)trimethylammonium) bis(trifluoromethylsulfonyl)imide (choline bistriflimide) was obtained as a supercooled liquid at room temperature (melting point = 30 degrees C). Crystals of choline bistriflimide suitable for structure determination were grown from the melt in situ on the X-ray diffractometer. The choline cation adopts a folded conformation, whereas the bistriflimide anion exhibits a transoid conformation. The choline cation and the bistriflimide anion are held together by hydrogen bonds between the hydroxyl proton and a sulfonyl oxygen atom. This hydrogen bonding is of importance for the temperature-dependent solubility proper-ties of the ionic liquid. Choline bistriflimide is not miscible with water at room temperature, but forms one phase with water at temperatures above 72 degrees C (equals upper critical solution temperature). H-1 NMR studies show that the hydrogen bonds between the choline cation and the bistriflimide anion are substantially weakened above this temperature. The thermophysical properties of water-choline bistriflimide binary mixtures were furthermore studied by a photopyroelectric technique and by adiabatic scanning calorimetry (ASC). By photothermal analysis, besides highly accurate values for the thermal conductivity and effusivity of choline bistriflimide at 30 degrees C, the detailed temperature dependence of both the thermal conductivity and effusivity of the upper and lower part of a critical water-choline bistriflimide mixture in the neighborhood of the mixing-demixing phase transition could be determined with high resolution and accuracy. Together with high resolution ASC data for the heat capacity, experimental values were obtained for the critical exponents alpha and beta, and for the critical amplitude ratio G(+)/G(-). These three values were found to be consistent with theoretical expectations for a three dimensional Ising-type of critical behavior of binary liquid mixtures.

Crystal polymorphism in 1-butyl-3-methylimidazolium halides: supporting ionic liquid formation by inhibition of crystallization

Crystallization of 1-butyl-3-methylimidazolium chloride from mixed ionic liquid or ionic liquid-aromatic solution, and from the melt yields different crystalline polymorphs, the first direct evidence for inhibition of crystallization in ionic liquids by polymorphism.

Crystal structures of imidazolium bis(trifluoromethanesulfonyl)imide 'ionic liquid' salts: the first organic salt with a cis-TFSI anion conformation

Crystal structures of two examples of an important class of ionic liquids, 1,3-dimethylimidazolium and 1,2,3-triethylimidazolium bis(trifluoromethanesulfonyl)imide have been characterized by single crystal X-ray diffraction. The anion in the 1,3-dimethylimidazolium example (mp 22 degreesC), adopts an unusual cis-geometry constrained by bifurcated cation-anion C-H...O hydrogen-bonds from the imidazolium cation to the anion resulting in the formation of fluorous layers within the solid-state structure. In contrast, in the 1,2,3-triethylimidazolium salt (mp 57 degreesC), the ions are discretely packed with only weak C-H...O contacts between the ions close to the van der Waals separation distances, and with the anion adopting the twisted conformation observed for all other examples from the limited set of organic bis( trifluoromethanesulfonyl) imide crystal structures. The structures are discussed in terms of the favorable physical properties that bis(trifluoromethanesulfonyl) imide anions impart in ionic liquids.

The solution structure of 1:2 phenol/N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide liquid mixtures

Neutron diffraction has been used to investigate the liquid structure of a 1:2 solution of phenol in the ionic liquid N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide at 60 ◦C, using the empirical potential structure refinement (EPSR) process to model the data obtained from the SANDALS diffractometer at ISIS. Addition of phenol results in suppression of the melting point of the pyridinium salt and formation of a room temperature solution with aromatic phenol–cation and phenol-OH to anion hydrogen-bonding interactions.

Association and liquid structure of pyridine-acetic acid mixtures determined from neutron scattering using a ‘free proton’ EPSR simulation model

The liquid structure of pyridine-acetic acid mixtures have been investigated using neutron scattering at various mole fractions of acetic acid, χHOAc = 0.33, 0.50, and 0.67, and compared to the structures of neat pyridine and acetic acid. Data has been modelled using Empirical Potential Structure Refinement (EPSR) with a ‘free proton’ reference model, which has no prejudicial weighting towards either the existence of molecular or ionised species. Analysis of the neutron scattering results shows the existence of hydrogen-bonded acetic acid chains with pyridine inclusions, rather than the formation of an ionic liquid by proton transfer.

Non-ideal behaviour of a room temperature ionic liquid in an alkoxyethanol or poly ethers at T = (298.15 to 318.15) K

Non-ideal behaviour of 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] in ethylene glycol monomethyl ether; CH3OCH2CH2OH (EGMME), ethylene glycol dimethyl ether; CH3OCH2CH2OCH3 (EGDME) and diethylene glycol dimethyl ether; CH3(OCH2CH2)2OCH3 (DEGDME) have been investigated over the whole composition range at T = (298.15 to 318.15) K. To gain insight into the mixing behaviour, results of density measurements were used to estimate excess molar volumes, image, apparent molar volumes, Vphi,i, partial molar volumes, image, excess partial molar volumes, image, and their limiting values at infinite dilution, image, image, and image, respectively. Volumetric results have been analyzed in the light of Prigogine–Flory–Patterson (PFP) statistical mechanical theory. Measurements of refractive indices n were also performed for all the binary mixtures over whole composition range at T = 298.15 K. Deviations in refractive indices ?phin and the deviation of molar refraction ?xR have been calculated from experimental data. Refractive indices results have been correlated with volumetric results and have been interpreted in terms of molecular interactions. Excess properties are fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors.

Prediction of ionic liquid properties. I. Volumetric properties as a function of temperature at 0.1 MPa

The prediction of molar volumes and densities of several ionic liquids has been achieved using a group contribution model as a function of temperature between (273 and 423) K at atmospheric pressure. It was observed that the calculation of molar volumes or densities could be performed using the "ideal" behavior of the molar volumes of mixtures of ionic liquids. This model is based on the observations of Canongia Lopes et al. (J. Phys. Chem. B 2005, 109, 3519-3525) which showed that this ideal behavior is independent of the temperature and allows the molar volume of a given ionic liquid to be calculated by the sum of the effective molar volume of the component ions. Using this assumption, the effective molar volumes of ions constituting more than 220 different ionic liquids were calculated as a function of the temperature at 0.1 MPa using more than 2150 data points. These calculated results were used to build up a group contribution model for the calculation of ionic liquid molar volumes and densities with an estimated repeatability and uncertainty of 0.36% and 0.48%, respectively. The impact of impurities (water and halide content) in ionic liquids as well as the method of determination were also analyzed and quantified to estimate the overall uncertainty. © 2008 American Chemical Society.

Liquid structure of the ionic liquid 1,3-dimethylimidazolium bis{(trifluoromethyl)sulfonyl}amide

Neutron diffraction has been used to determine the liquid structure of 1,3-dimethylimidazolium bis{( trifluoromethyl) sulfonyl} amide ([dmim][NTf2]). Significantly smaller charge ordering is found in this liquid compared with analogous chloride and hexafluorophosphate salts due to the diffuse charge density and size of the [NTf2](-) anion. This is manifested in a much larger cation-cation and cation-anion separation and an overlap of the cation-cation and cation-anion shells. Comparison of the liquid structure with the crystal structure reported by Holbrey et al. ( Dalton Trans. 2004, 2267) indicates little correlation, for example, the [NTf2](-) anion adopts a trans orientation predominantly in the liquid whereas a cis orientation is found in the solid phase.