Solvatochromic parameters for binary mixtures of an ionic liquid with various protic molecular solvents

Abstract  

Solvatochromic parameters (E _T ^N, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) have been determined for binary mixtures of propan-2-ol, propan-1-ol, ethanol, methanol and water with recently synthesized ionic liquid (IL; 2-hydroxyethylammonium formate) at 25 °C. In all solutions except aqueous solution, E _T ^N values of the media increase abruptly with the ILs mole fraction and then increase gradually to the value of pure IL. A synergistic behavior is observed for the α parameter in all solutions. The behavior of π* and β are nearly ideal for all solutions except for solutions of methanol with the IL. The applicability of nearly ideal combined binary solvent/Redlich–Kister equation was proved for the correlation of various solvatochromic parameters with solvent composition. The correlation between the calculated and the experimental values of various parameters was in accordance with this model. Solute–solvent and solvent–solvent interactions were applied to interpret the results.     

Solvatochromic parameters for binary mixtures of an ionic liquid with various protic molecular solvents

Abstract  Solvatochromic parameters (E _T ^N, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) have been determined for binary mixtures of propan-2-ol, propan-1-ol, ethanol, methanol and water with recently synthesized ionic liquid (IL; 2-hydroxyethylammonium formate) at 25 °C. In all solutions except aqueous solution, E _T ^N values of the media increase abruptly with the ILs mole fraction and then increase gradually to the value of pure IL. A synergistic behavior is observed for the α parameter in all solutions. The behavior of π* and β are nearly ideal for all solutions except for solutions of methanol with the IL. The applicability of nearly ideal combined binary solvent/Redlich–Kister equation was proved for the correlation of various solvatochromic parameters with solvent composition. The correlation between the calculated and the experimental values of various parameters was in accordance with this model. Solute–solvent and solvent–solvent interactions were applied to interpret the results. Graphical Abstract  Predicted values of solvatochromic parameters (SP) (E _T ^N, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) from the correlation equations versus its experimental values for binary mixtures of 2-hydroxyethylammonium formate with water, methanol, ethanol, propan-1-ol and propan-2-ol.      

An enthalpic approach to delineate the interactions of cations of imidazolium-based ionic liquids with molecular solvents

We present a systematic investigation on the enthalpic assessment of the interactions operating between the cation and anion of four imidazolium ionic liquids with aqueous and various nonaqueous solvents. Accurate experimental information gathered with the help of an isothermal titration calorimeter at 298.15 K has been analyzed for excess partial molar enthalpy of the ionic liquid, H(IL)(E), in terms of hydrophobic and solvation effects. The variations in the limiting excess partial molar enthalpy of the ionic liquid, H(IL)(E, ∞), have been correlated with solvent properties. We have quantified the enthalpic effects due to dissociation of ionic liquids in very dilute solutions and to clathrate formation with the increasing concentration of ionic liquid. A change in enthalpic behavior from endothermic to exothermic is observed on increasing the carbon chain length attached to the imidazolium ring. The solvent reorganization around the cationic species has been unraveled by employing the ionic liquid interaction parameters called as H(IL-IL)(E) deduced from the H(IL)(E) data. The apparent relative molar enthalpy, φ(L), derived from H(IL)(E) data has been examined in the light of the specific ion interaction theory as advanced by Pitzer with accurate results.     

Self-assembly via ionic interactions of calix[6]arene-based receptors displaying remarkable host-guest properties toward neutral guests

The association of a C_3v-symmetrical calix[6]tris-amine with different concave tris-carboxylic acids of various degrees of flexibility has been explored by ¹H NMR spectroscopy. In all cases, self-assembled structures directed by the selective inclusion of a neutral guest molecule were obtained, the more preorganized being stable in protic solvents. With a rigid C₃-symmetrical cap, chiral guest recognition in the calixarene cavity resulted. A large tris-acidic partner gave a unique molecular ditopic receptor that is able to simultaneously accommodate two neutral molecules in two distinct hydrophobic cavities with different binding processes.     

Intermolecular interactions of 1-vinyl-1,2,4-triazole in various solvents

The solvent effect on intermolecular interactions of 1-vinyl-1,2,4-triazole was estimated by ¹H NMR spectroscopy. It was shown that 1-vinyl-1,2,4-triazole molecules form homoassociates (molecular stacks) which are broken on dilution with CCl₄. In polar solvents (dimethylacetamide-d ₆, D₂O), monomer-solvent heteroassociates prevail.     

Guest encapsulation and self-assembly of molecular capsules in polar solvents via multiple ionic interactions

Herein we report the formation and characterization of a novel type of capsules resulting from the self-association between oppositely charged complementary building blocks in MeOH/H2O. The assembly is based on the interaction between tetraamidinium calix[4]arenes 1a-d and tetrasulfonato calix[4]arene 2. Evidence for the formation of the expected 1:1 assemblies is provided by proton NMR, ESI-MS, and ITC. The association process is fast on the NMR time scale and strongly entropy driven, with association constants in the range of 10(6) M-1. The system 1a.2 shows binding affinity toward acetylcholine, tetramethylammonium, and N-methylquinuclidinium cations.     

Selection and design of ionic liquids as solvents in extractive distillation and extraction processes

Since the late 1990’s there has been a tremendous growth in literature on ionic liquids (ILs) for a broad range of applications, i.e. catalysis, electrolytes for batteries, in solvolysis of biomass, and also in separation technology. ILs can be applied as solvents for absorption (e.g. of CO₂), extractive distillation and extraction processes. That ILs are not magic solvents but have their limitations has also become evident during the past years. Especially the high costs associated with ILs and the lack of experience with these materials in the industrial practice are factors limiting industrial adoption of ILs. The often praised versatility of properties that can be achieved through combination of different cations and anions generates a huge amount of options and makes it difficult to decide where to start when selecting/designing a solvent. This paper focuses on solvent selection/design for applications in extractive distillations and liquid-liquid extractions; also, solvent performance in several specific case studies taken from the open literature is discussed. Important recommendations include: a) make a conceptual process design including the recovery step, regeneration of the IL may be a critical parameter; b) if extractions from aqueous streams are studied, the uptake of water by the IL is an important factor because such co-extracted water is evaporated during the regeneration; c) compare the process with conventional processes to check whether it performs better than the state-of-the-art in industry.     

Structures of ionic species and electronic interactions in radical ions; ketyls with divalent cations

EPR and optical spectra of magnesium and calcium ketyls were investigated in MTHF and mixtures of DMF and MTHF at various concentrations. It was shown that these ketyls form aggregates in ethereal solvents and dissociate into biradicals in more polar solutions. Models of ion aggregate to explain the observed EPR and optical spectra are suggested.     

Application of density functional theory and vibrational spectroscopy toward the rational design of ionic liquids

Density functional theory methods in combination with vibrational spectroscopy are used to investigate possible variants of molecular structure of the ion pairs of several imidazolium-based ionic liquids (ILs). Multiple stable structures are determined with the anion positioned (a) near to the C2 atom of the imidazolium ring, (b) between N1 and C5, (c) between N3 and C4, and (d) between C4 and C5. Chloride and bromide anions in vacuum also occupy positions above or below the imidazolium ring, but in the condensed state these positions are destabilized. In comparison with the halides that almost equally occupy the positions (a-d), tetrafluoroborate and hexafluorophosphate anions strongly prefer position (a). The position and the type of the anion influence the conformation of the side chains bound to the imidazolium N1 atom, which are able to adopt in vacuum all usual staggered or eclipsed conformations, although in the liquid state some of the conformations are present only as minor forms if at all. Vibrations of the cations depend both on the conformational changes and on the association with the anion. The formation of the ion pairs influences mainly stretching and out-of-plane vibrations of the imidazolium C-H groups and stretching vibrations of the perfluoroanions. Other modes of the ions retain their individuality and practically do not mix. This allows "interionic" vibrations to be separated and to regard the couple of the ions as an anharmonic oscillator. Such a model correlates the molecular structure of various ILs and their melting points without involving the energy of the interaction between the cations and anions but explains structure-melting point correlations on the grounds of quasy-elastic properties.     

Effect of water and organic solvents on the ionic dissociation of ionic liquids

The effect of water and several organic solvents on the density, viscosity, and conductivity of ionic liquids (ILs) 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), 1-n-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), and 1-n-butyl-3-methylimidazolium trifluoroacetate ([bmim][CF3CO2]) was studied at 298.15 K in wide composition ranges. The density, viscosity, and conductivity of the three neat ILs were also determined at various temperatures. Upon the basis of the molar conductivity of the mixtures and that of the neat ILs of the same viscosity, the degree of dissociation of ILs in the solutions was investigated. It can be deduced that the organic solvents enhance the ionic association of the ILs, the effect depending on the solvent dielectric constant, while water promotes dissociation significantly due to its high dielectric constant and its ability to form strong hydrogen bonds with the anions of the ILs.     

Autooxidation of hydrocarbons with oxygen in ionic liquids as solvents

The results of hydrocarbons autooxidation process carried out using several ionic liquids (IL) as solvents are demonstrated. Test studies to check the influence of ILs on this process showed that most ILs can accelerate the initiation rate of autooxidation. The results could be very useful for choosing an IL not only for autooxidation processes but also for catalytic oxidation systems. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 287–293, 2008     

Preparation of substituted ionic carbohydrate polymers and their interactions with ionic surfactants

The formation of micelles of hexadecyltrimethylammonium chloride (CTAC) and sodium dodecylsulfate (SDS) in aqueous solutions containing charged polysaccharides was studied by steady-state and time-resolved fluorescence measurements using pyrene as a photophysical probe. Micropolarity studies using the I₁/I₃ ratio of the vibronic emission bands of pyrene and the behaviour of the I_E/I_M ratio between the excimer and monomer emissions show the formation of hydrophobic domains. The interactions between the polyelectrolytes and surfactants of opposite charge lead to the formation of induced pre-micelles at surfactant concentrations lower than the critical micellar concentration (cmc) of the surfactants. At similar concentrations, the I_E/I_M ratio shows a peak. This aggregation process is assumed to be due to electrostatic attractions. At higher surfactant concentrations, near the critical micellar concentration, micelles with the same properties as those found in pure aqueous solution are formed. On the other hand, systems containing polyelectrolytes and surfactants of the same charge do not show this behaviour at low concentrations. The presence of long alkyl chains bound to the polyelectrolytes also induces the formation of free micelles at concentrations somewhat below the aqueous cmc.     

Thermochemistry of mixing imidazole-based ionic liquids with water and organic solvents

The results of the calorimetric studies of the enthalpies of mixing of some ionic liquids, 1-butyl-3-methylimidazolium chloride and acetate, with water, pentanol, dimethyl sulfoxide and dimethylformamide are presented. Protic solvents interact with the ionic liquid anion, wheras aprotic, with the cation. The mixing enthalpy depends on the dissociation degree of the ionic liquid.     

Diffusion of ionic species labeled with35S in various aqueous electrolyte solutions at 25°C

Composite diffusion coeffcients have been measured for the various species labeled with³⁵S which are present in a number of aqueous solutions due to the introduction of the labeled material as³⁵SO ₄ ^2– . The solutions were of two components consisting of water and either sodium sulfate. The diffusion coeffcient measured for sodium chloride solutions is similar to literature data for the corresponding diffusion in sodium sulfate solutions. The results for sulfuric acid and ammonium hydrogen sulfate have been interpreted using literature data for the relative concentrations of the hydrogen sulfate and sulfate ions to obtain estimates for the diffusion coefficents of those ions. The results for perchloric acid, regarded as representing the diffusion coefficient of the hydrogen sulfate ion, have a much different concentration dependence to that observed for the estimates for that ion in sulfuric acid and ammonuim hydrogen sulfate. The difference is attributed to the effect of the perchlorate ion on the water structure.     

The possible role of ionic species in selective biodistribution of photochemotherapeutic agents toward neoplastic tissue

Photochemotherapeutic agents are photosensitizers that are selectively retained by neoplastic tissue. When tumor tissue containing these drugs is irradiated with visible electromagnetic radiation, the photosensitizing reaction may lead to tumor eradication, termed photodynamic therapy. Exogenous photosensitizers commonly used in clinical trials are mainly porphyrin derivatives. Phthalocyanines are currently being investigated as "second generation" photochemotherapeutic agents. The mechanism by which these photosensitizers are selectively retained in neoplastic tissue is unclear. This review examines the role of tissue and cellular pH as a factor in selective biodistribution. The pH values of normal and tumor tissue are summarized and the ionic species distribution diagram of porphyrins is presented. A two-fold mechanism of selective biodistribution is advanced, one involving normal tissue vs. tumor tissue selectivity, the other involving intracellular vs. intercellular distribution of sensitizer ionic species.     

Reactions of 1,2,3-triphenylcyclopropene with N-bromosuccinimide in various polar solvents

Conclusions A study was made of the reactions of 1,2,3-triphenylcyclopropene with N-bromosuccinimide in alcohol, acetic acid, aqueous DME, and also anhydrous DMSO. The direction and stereochemistry of these reactions were established.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 234–237, January, 1977.