Pentafluoroethyl(fluoro)phosphate ionic liquids: synthesis and properties.

During the last decade there has been an explosion of interest in ionic liquids. If the keywords “ionic liquid” or “ionic liquids” are used for a literature research in the Web of Science, more than seven thousand entries can be found for 2011. That is a tenfold increase in the number of publications dealing with ionic liquids over the past decade, and the field shows no signs of slowing down. Ionic liquids have changed from a lab curiosity to materials of tremendous academic and industrial interest. This new and remarkable liquid substance with unique and fascinating properties offers a phenomenal opportunity for new science and technology. The interest in these new materials is due to their wide range of possible applications as solvents for reaction and material processing, as extraction media or as working fluids in mechanical applications. Originating in the field of electrochemistry and based upon their wide electrochemical windows and good conductivities, ionic liquids have found useful applications in sensors, solar cells, solid-state photocells, batteries, separation devices and as thermal fluids, lubricants, hydraulic fluids, ionogels and fuels. The generally accepted definition of an ionic liquid is a salt composed solely of ions with melting points below 100 °C. New combinations of ions provide changing physical properties and thus novel potential applications for this class of liquid material. To a large extent, the structure and properties of ionic liquids are determined by the intermolecular interaction between anions and cations. In particular, the subtle balance between Coulomb forces, hydrogen bonds, π stacking and repulsion–dispersion forces is of great importance for understanding the properties of ionic liquids. All the important properties such as structure, diffusion, viscosity, conductivity or melting points depend on these interactions between cations and anions in ionic liquids. Thus, an important goal is to develop a fundamental understanding of their chemical and physical properties at the molecular level. Reliable structure–property relationships can help us to synthesize ionic liquid compositions with the desired set of properties. Since 2005 a number of research programs have been set up worldwide to advance ionic liquids research. Among those, the Japanese Priority Area “Science of Ionic Liquids” running from 2005 to 2009 and the priority programme SPP 1191 “Ionic Liquids” implemented by the German Science foundation (DFG) in 2006 and finished at the end of this year may be the most prominent ones in the academic arena. The efforts and developments achieved in ionic liquids research from these and other programmes are presented in this special issue. On the occasion of the International Bunsen Meeting 2012 in Leipzig, we put together a collection of almost forty articles that show the growing diversity within the field. In this special issue of ChemPhysChem, developments in experiment, theory and simulations for investigating ionic liquids are presented. The articles highlight the interaction within ionic liquids between anions and cations studied by a variety of experimental and theoretical methods including spectroscopy, ab initio simulations, classical molecular dynamics simulations and quantum molecular dynamics simulations. A particular focus is put on hydrogen bonding and dispersion forces, which are often assumed to be unimportant in Coulomb systems but are absolutely crucial to understanding ionic liquids. The critical review of theoretical and simulation approaches for describing the properties of ionic liquids is an important issue in this respect. Another topic is the interaction of ILs with water and organic solvents leading to modified local structures and polarities (Figure 1). In general, IL mixtures with water, alcohols and amines allow interesting tuning of important IL physical properties, including structural and transport properties such as diffusion coefficients, viscosities and conductivities. Walden plots, which compare the molar conductivity as a function of fluidity (inverse viscosity), show deviations from ideal, linear behaviour derived from well-understood aqueous solutions. Ionic liquids in its pure state (left) and in a mixture with an organic solvent (blue). Why not consider mixing ILs themselves to change properties? Thus another focus is put on mixtures of ILs including different anion–cation combinations. By varying the cation or the anion only, structure and interaction strength can be modified in the desired way. Several examples are given for structure–property relations in ionic liquids, which may allow predictions for physical properties for a set of specially synthesized ILs. Chemical reactions and coordination in ionic liquids are also attracting increasing interest. In several articles the effects on physical properties of other materials such as gels and micelles in IL environments are reported. ILs have also become increasing important in biology. The behaviour of biomolecules, such as the folding and unfolding of proteins, are developing into an important facet in ionic liquids research. Of course, after having an idea about the origin of the physical properties, new ionic liquids need to be synthesized and characterized. New and special ionic liquids and their properties are introduced in some of the contributions. An important aspect in and of itself is the liquid/gas or the liquid/liquid interface of ionic liquids (Figure 2). How do these interfaces look like with respect to the polar and hydrophobic parts of anions and cations? How do the IL properties change at the interfaces? Combinations of experimental and theoretical methods try to provide answers to these questions. Ion-pair evaporating from the surface of an imidazolium-based ionic liquid. All these fundamental issues are addressed in this special issue of ChemPhysChem. We hope that this compilation improves our understanding of the fascinating physical chemistry of ionic liquids. An understanding at the molecular level opens new potential for fundamentals and applications. Ralf Ludwig 1 Ed Maginn 1 Bala Sundaram 1

Ionic liquids have received considerable attention by the chemical industry in recent years, mostly towards the development of environmentally benign processes. In this work, microscopic structure, dynamic and thermodynamic properties of imidazolium-based ionic liquids are calculated using theoretical models that cover a wide range of length and time scales, from ab initio density functional theory (DFT) calculations to atomistic molecular simulation and finally to a macroscopic equation of state based on perturbation theory. Different ionic liquids and polar solvents are examined and calculations are performed over a wide range of conditions. Model calculations are compared against literature experimental data. In all cases, the agreement between experiment and calculations/theory is very good. Thus, it is verified that carefully selected models can be used for reliable estimation of properties, even in the absence of experimental measurements.

Densities, viscosities and derived thermophysical properties of water-saturated imidazolium-based ionic liquids

Ionic liquids (ILs) hold great promise in many fields including energy storage and generation, mechanical, pharmaceutical, synthetic and separation applications to name just a few. For any given application, the desired physical properties of the ideal IL may differ substantially from others and no widely applicable patterns or trends to facilitate intuitive design. The origins of physical properties lie in the characteristics of the intermolecular energetics, which consist of a complex interplay between electrostatic and dispersion forces. This thesis investigates and develops computational methodologies for calculating a reliable description of the intermolecular interactions for this challenging class of solvents and electrolytes of the future. The electrostatic approximation used in classical molecular dynamics (MD) where atomic partial charges are assigned was investigated in terms of methods based on density matrix partitioning, and the restrained electrostatic potentials (RESP) approaches. It was found that the “geodesic” atomic partial charge scheme, part of the RESP family, produced the most accurate charges. This was measured in terms of (a) charge convergence with increasing basis set size; (b) charge invariance with changes to the coordinate system; (c) insensitivity to minor structural changes on the resulting charges; (d) adequate capture of charge transfer effects; and (e) the preservation of symmetric of charges in symmetric molecules. Although charges can vary dramatically depending on the scheme used, the careful use of atomic partial charge schemes may still produce reliable forcefields, or at least serve as a rapid diagnostic tool to quantify electrostatic interactions and charge transfer. In moving towards unbiased a priori descriptions of IL intermolecular interactions, second-order Moller-Plesset perturbation theory (MP2) was used with the linear-scaling fragment molecular orbital (FMO) framework to assess the extent to which dispersion forces play a role in the intermolecular energetics. ILs of increasing size were examined such that the many-body effects may be captured. The dispersion energy contribution formed up to 20% of the total interaction energy. Furthermore, the interaction energy as produced by FMO was within 1 kJ mol−1 of the full-wavefunction MP2 interaction energy when three-body effects were included. As the dispersion interaction is purely a quantum mechanical phenomenon, correlated quantum mechanical methods, such as MP2 or coupled-cluster approaches, are required to provide an unbiased account of these effects. Ab initio methods such as MP2 and CCSD(T) scale formally as N⁵ an N⁷, respectively, with chemical system size. While the FMO approach provides a marked improvement in efficiency, the counterpoise (CP) approach to correcting the basis set superposition error (BSSE) is not amenable to fragmented approaches and requires each ion in the cluster to be calculated in the basis set of the entire system. In order to remove this bottleneck, the spin-component scaled second-order Moller Plesset perturbation theory (SCS-MP2) methodology was refined by fitting 174 non-CP corrected interaction energies at the MP2/cc-pVTZ level of theory to CP corrected CCSD(T)/CBS benchmark energies. This has resulted in an implicit BSSE correction that may be used within the highly efficient FMO framework, and is shown to yield results on par with or exceeding the accuracy of MP2/cc-pVQZ for clusters of two and four ion pairs (IPs). This new approach as been termed SCS-IL-MP2. An alternative dispersion corrected density functional theory (DFT) approach, DFT- D3, was assessed and refined in view of producing accurate interaction energies at the same CCSD(T)/CBS quality. The same test set of 174 ILs was used to fit the SCS-IL-MP2 approach was used to refit the DFT-D3 approach for both the Hartree-Fock (HF) wavefunction and the PBE and BLYP density functionals (DFs). In most cases, the selection of the DF and associated DFT-D version 3 (DFT-D3) parameters differed negligibly with all reaching within 1 to 2 kJ mol−1 per IP. HF-D3 parameters, on the other hand, showed a substantial improvement, particularly when used with the Becke-Johnson (BJ) damping function. Refitted HF-D3 and the BJ damping function was able to consistently provide interaction energy errors below 5 kJ mol−1 per IP. It would be worthwhile further investigating the application of the refined HF-D3 in its ability to produce reliable energies and geometries over a more diverse set of ILs. Both the SCS-IL-MP2 and new DFT-D3 approaches may be applied to the highly scal- able FMO framework. These form the core elements of the quantum chemistry toolbox for the study and understanding of the physicochemical properties of ILs that have so far been only superficially characterised by electronic structure theory. From this starting point, a rigorous and unbiased a priori understanding of the intermolecular interactions and resulting physicochemical properties may be predicted by means of efficient ab initio molecular dynamics (AIMD) techniques.

A new three-parameter (valency, ion size, and charge asymmetry) model, the asymmetric restricted primitive model (ARPM) of ionic liquids, has recently been proposed. Given that ionic liquids generally are composed of monovalent species, the ARPM effectively reduces to a two-parameter model. Monte Carlo (MC) simulations have demonstrated that the ARPM is able to reproduce key properties of room temperature ionic liquids (RTILs) in bulk and at charged surfaces. The relatively modest complexity of the model raises the possibility, which is explored here, that a classical density functional theory (DFT) could resolve its properties. This is relevant because it might generate great improvements in terms of both numerical efficiency and understanding in the continued research of RTILs and their applications. In this report, a DFT for rod-like molecules is proposed as an approximate theoretical tool for an ARPM fluid. Borrowing data on the ion pair fraction from a single bulk simulation, the ARPM is modelled as a mixture of dissociated ions and connected ion pairs. We have specifically studied an ARPM where the hard-sphere diameter is 5 Å, with the charge located 1 Å from the hard-sphere centre. We focus on fluid structure and electrochemical behaviour of this ARPM fluid, into which a model electrode is immersed. The latter is modelled as a perfect conductor, and surface polarization is handled by the method of image charges. Approximate methods, which were developed in an earlier study, to take image interactions into account, are also incorporated in the DFT. We make direct numerical comparisons between DFT predictions and corresponding simulation data. The DFT theory is implemented both in the normal mean field form with respect to the electrostatic interactions and in a correlated form based on hole formation by both steric repulsions and ion-ion Coulomb interactions. The results clearly show that ion-ion correlations play a very important role in the screening of the charged surfaces by our ARPM ionic liquid. We have studied electrostatic potentials and ion density profiles as well the differential capacitance. The mean-field DFT fails to reproduce these properties, but the inclusion of ion-ion correlation by a simple approximate treatment yields quite reasonable agreement with the corresponding simulation results. An interesting finding is that there appears to be a surface phase transition at relatively low surface charge which is readily explored by DFT, but seen also in the MC simulations at somewhat higher asymmetry.

A review of group contribution models to calculate thermodynamic properties of ionic liquids for process systems engineering

Recent advances for sustainable production of levulinic acid in ionic liquids from biomass: Current scenario, opportunities and challenges

Ionic liquids (ILs) are a unique class of electrolytes, which characteristics make them suitable for use in solar cells, supercapacitors, and fuel cells1. Due to the appealing properties such as good electrochemical stability, low vapour pressure, high concentration of ions and the lack of solvent, they have been under intense study since the early 2000s. Although numerous theoretical2,3, computational4,5, and experimental studies6,7 have shed light on the interfacial properties of ILs, which differ noticeably from the aqueous electrolytes, multiple open questions remain. One such problem is how the interfacial capacitance is affected by the ambient temperature, as studies have shown both positive and negative temperature dependences8,9. Understanding the temperature dependence of interfacial capacitance is crucial as it is relevant for the description of energy storage and is one of the few quantities, which can be estimated both experimentally and computationally.In this study, we combine the density functional theory (DFT) calculations with molecular dynamics (MD) simulations of graphene (Gr) | EMImBF4 IL interface to explain the effect of temperature on capacitance. MD simulations allow us to investigate the probable distribution of ions near the electrode’s surface and relate the changes of ILs structure to the capacitance using the interfacial bilayer model (IBL). We show that the increase of temperature affects the capacitance near the potential of zero charge by attenuating the overscreening without a notable change in the IL interfacial structure. The characteristic peaks and plateaus in the capacitance potential dependence are explained through the concepts of IL layering and saturation of the second IL layer described in the IBL. Using the DFT calculations, we estimate the impact of the quantum capacitance of Gr on the total interfacial capacitance and its temperature dependence. By accounting for the limiting quantum capacitance, the total interfacial capacitance was significantly altered in the case of the Gr electrode, as the effect of the temperature was dampened, and a V-shaped capacitance curve was obtained.Acknowledgements:This work was supported by the Estonian Research Council grant PSG249 and by the EU through the European Regional Development Fund under project TK141 (2014-2020.4.01.15-0011). The financial support from FCT/MCTES through the Portuguese national funds, project No. UID/QUI/50006/2021 (LAQV@REQUIMTE) is also acknowledged.

Most theoretical studies of the properties of an electrolyte, including an ionic liquid, treat the electrolyte as a mixture of charged hard spheres in a solvent modeled as a dielectric continuum. However, ionic liquids generally consist of nonspherical ions that are not dissolved in a solvent. A simple extension of the primitivel model of electrolytes is to represent an ionic liquid as a mixture of charged hard spheres (negative monovalent ions in our case) and nonspherical ions consisting of a dimer of two touching hard spheres, one of which is charged (monovalent and positive in our case) and the other is neutral. This simple model has been used previously by Federov et al. and by ourselves. Here, we use the classical density functional theory to study the interfacial properties of the model ionic liquid over a range of electrode charges and two electrolyte concentrations. For simplicity, all of the spheres have the same diameter. In contrast to the simulations of Federov and Kornyshev, we find that a plot of the differential capacitance of the dimer electrolyte versus the surface potential typically exhibits only a single hump. Also, differing from the studies of Lamperski et al. for a spherical electrolyte, which showed a decline of the maximal differential capacitance as the ionic concentration decreases, the maximum of the differential capacitance of the dimer electrolyte increases slightly with decreasing ionic concentration. Our theoretical results show other unexpected effects of the geometry of ionic species on the electrochemical properties of the electric double layer of an ionic liquid.

Room temperature ionic liquids (RTILs), considered as designers' solvents, are attracting a great attention because of their possibility to be tailored based on property requirements. The ionic liquids designed and synthesized for carrying out specified task are referred as functionalized ionic liquids, which show great application potential in various processes. The efforts to produce functionalized ionic liquids, characterize them, and evaluate their properties and applications are presented in this thesis. In chapter 1 the recent developments in ionic liquid functionalization are highlighted. Chapter 2 describes the synthesis and characterization of imidazolium salts in which a nitrile group is attached to the alkyl side chain (single-armed as well as double-armed). The nitrile group was chosen as it is a promising donor to transition metals such as palladium and platinum. The physicochemical properties of these new ionic liquids are described and it is shown how the length of the alkyl unit linking the imidazolium ring and the CN group influences the melting point of the ionic liquid. The third chapter describes palladium complexation reactions with the nitrile functionalized imidazolium ionic liquids (prepared as described in Chapter 2). Their application in C-C coupling and hydrogenation reactions are described. It will be shown that the palladium complexes serve as precursors to nanoparticle catalyst reservoirs and are very efficiently stabilized by the nitrile-functionalized ionic liquids. In chapter 4, the synthesis of a series of nitrile functionalized ionic liquids based on the N-butylnitrile pyridinium cation is reported and their suitability as solvents for palladium-catalyzed biphasic Suzuki and Stille coupling reactions is demonstrated. TEM images reveal that nanoparticles are formed in situ in Stille reactions and show that the nitrile-functionalized ionic liquid exert a superior nanoparticle-stabilizing effect compared to non-functionalized ionic liquids. This allows excellent catalyst lifetimes. In the fifth chapter the synthesis and characterization of a series of ionic liquids incorporating the allyl functionality and some nascent reactions that they undergo, indicating that they are useful precursors to a wide range of other functionalized ionic liquids, will be described. Chapter 6 reports on a concept of dual-functionalized ionic liquids. Specifically imidazolium cations with various functionalities are combined with the nitrile functionalized anion [CH3CH(BF3)CH2CN]-, aiming at reducing the melting point and visocity of ionic liquids. In the final chapter the ionic liquid, 1-methyl-3-(4-vinylbenzyl)-imidazolium chloride, is prepared and polymerized to form a macromolecule that is subsequently used as a transition metal nanoparticle stabilizer. A methodology that enables transition metal nanoparticle transfer between liquid phases, via surface modification of the nanoparticles by anion exchange, is described.

10.31635/ccschem.021.202101063

In order to increase the solubility of ionic liquids in base oils and to improve the lubricating performance of light alloys, two new ionic liquids comprised of sulfonate base anion and phosphonium based cation are designed and synthesized. The difference between these two ionic liquids is the cation: One has only one organophosphate group (P88816DOSS) and the other has two organophosphate group (P888PDOSS). The copper strip corrosion test is used to evaluate the anticorrosion properties of new developed ionic liquids. Tribological properties of the ionic liquids are investigated by an optimal SRV‐IV oscillating tribometer. The results indicate that the new designed ionic liquids show very good solubility in traditional mineral‐based oils. P88816DOSS and P888PDOSS show excellent friction reduction, antiwear performance accompanied with effective anticorrosion properties for the mineral base oil. Surface analysis results show that the superior properties of P88816DOSS and P888PDOSS are attributed to surface chemical reactions between ionic liquids and light metal.

Polymerization of phenol with paraformaldehyde and catalytic sulfuric acid was carried out in room temperature ionic liquids based on imidazolium salts. The properties of ionic liquids were systematically varied by employing six different anions such as chloride, bromide, iodide, tetrafluoroborate, trifluoromethanesulfonate and hexafluorophosphate. In case of hydrophilic ionic liquids having chloride or bromide anion, phenol polymers with low molecular weight and narrow polydispersity were obtained. In contrast, using hydrophobic ionic liquids such as tetrafluoroborate and trifluoromethanesulfonate anions, high molecular weight phenol polymers were prepared. It is because interaction of the hydrophilic ionic liquids with phenol is stronger than that of the hydrophobic ionic liquids. The interaction between phenol and ionic liquids was investigated by 1H NMR measurements. Moreover, by using Brønsted acid ionic liquid carrying sulfuric acid moiety as a solvent, catalytic acid-free green polymerization of phenol with paraformaldehyde was accomplished. The ionic liquid was efficiently recovered and reused in new polymerization process of phenol.

Ionic liquids (ILs) are salts possessing many properties that make them attractive for use in a wide range of applications including batteries. One of the biggest drawbacks of ILs is that they tend to be more viscous than conventional solvents, which means low ionic conductivity when used as electrolytes in batteries. One effective way to lower the viscosities is to mix ILs with low viscosity additives such as molecular solvents. An obvious disadvantage of mixing molecular solvents with ILs is that the extremely low volatility of the IL is compromised by the finite vapor pressure of the diluent. One strategy to overcome this is to mix ILs with molecular solvents that are themselves of very low volatility. One such class of compounds are the glymes, which are oligoethers having a CH3O-(CH2CH2O)n-CH3 structure. In addition to having low volatility, glymes are effective at dissociating salts because of the electron donating nature of their ether oxygen groups. They also tend to have high thermal and electrochemical stability, which has led many groups to investigate mixing glymes with alkali metal salts (most commonly Li+ [NTf2]) for use as electrolytes in batteries. The alkali metal cation tends to coordinate with the oxygen atoms of the glyme, which can significantly lower the melting point of the salt. Such systems usually retain the attractive properties of pure ILs but the transport properties are improved. They are considered a new class of ILs and have been termed “solvate ILs”. Tetraethylene glycol dimethyl ether (tetraglyme or G4) is a particularly promising glyme. While there are many studies devoted to the properties of Li-based solvate ILs, much less work has been done investigating the properties of mixtures containing glymes and more conventional ionic liquids. In the current work, the density and viscosity of the IL [C6mim][NTf2]) and its mixtures with tetraglyme were measured at different temperatures and concentrations. Molecular dynamics (MD) simulations were also carried out on the mixtures in order to compute the density, self-diffusivity, viscosity, ideal ionic conductivity and liquid structure. We find that both the density and viscosity drop with increasing temperature and G4 concentration. Detailed analysis of the simulation results suggests that G4 preferentially solvates the cations, thereby weakening the interactions with the anions and resulting in faster dynamics, particularly for the anions. Such behavior was previously observed in solvate ionic liquids. Based on the simulation results of a model G4 system, it was further revealed that the localized negative charges on the oxygen atoms of G4 are primarily responsible for the preferential solvation of cations. If G4 (or a similar solvent) instead had large localized positive charges, it would tend to preferentially solvate the anions, resulting in increased cation mobility. This suggests a strategy for selecting molecular solvents that will selectively enhance cation dynamics.

Ionic liquids (ILs) are attractive alternatives to water, high temperature molten salts or conventional organic solvents for electrodeposition of technologically important metals. Designing ILs containing functional groups specifically targeted to interact with or even chelate metals, such as carboxylate, may increase the metal solubility and affect thermodynamic and electrochemical properties. This paper reports the synthesis and characterization of three ionic liquids comprised of one or two tetra-alkyl phosphonium cations paired with a hydrogen oxalate or oxalate anion, with the general formula [(PRRRR′)x][C2O4H2−x], R = 4,6 and R′ = 4, 14. These compounds were characterized by 1H, 13C, 31P NMR, and Raman spectroscopy. Electrochemical windows, electrical conductivities, densities and viscosities were also determined experimentally. Thermal gravimetric analysis (TGA) revealed decomposition temperatures above 200 °C and differential scanning calorimetry (DSC) analysis revealed that the two [(P66614)x][C2O4H2−x] salts have similar glass transition temperatures while [(P4444)2][C2O4] has a melting point above room temperature. Raman and powder X-ray diffraction spectroscopy confirm that Nd2O3 dissolves and complexes with [P66614][C2O4].