Molecular Architecture Effects on Bulk Nanostructure in Bis(Orthoborate) Ionic Liquids.

A series of 19 ionic liquids (ILs) based on phosphonium and imidazolium cations of varying alkyl-chain lengths with the orthoborate anions bis(oxalato)borate [BOB]- , bis(mandelato)borate, [BMB]- and bis(salicylato)borate, [BScB]- , are synthesized and studied using small-angle neutron scattering (SANS). All measured systems display nanostructuring, with 1-methyl-3-n-alkyl imidazolium-orthoborates forming clearly bicontinuous L3 spongelike phases when the alkyl chains are longer than C6 (hexyl). L3 phases are fitted using the Teubner and Strey model, and diffusely-nanostructured systems are primarily fitted using the Ornstein-Zernicke correlation length model. Strongly-nanostructured systems have a strong dependence on the cation, with molecular architecture variation explored to determine the driving forces for self-assembly. The ability to form well-defined complex phases is effectively extinguished in several ways: methylation of the most acidic imidazolium ring proton, replacing the imidazolium 3-methyl group with a longer hydrocarbon chain, substitution of [BOB]- by [BMB]- , or exchanging the imidazolium for phosphonium systems, irrespective of phosphonium architecture. The results suggest there is only a small window of opportunity, in terms of molecular amphiphilicity and cation:anion volume matching, for the formation of stable extensive bicontinuous domains in pure bulk orthoborate-based ILs. Particularly important for self-assembly processes appear to be the ability to form H-bonding networks, which offer additional versatility in imidazolium systems.

Transition anionic complex in trihexyl(tetradecyl)phosphonium-bis(oxalato)borate ionic liquid - revisited.

It was found that Li[BOB]·nH2O salts were not readily suitable for the synthesis of high-purity orthoborate-based tetraalkylphosphonium ionic liquids, as exemplified here for trihexyl(tetradecyl)phosphonium bis(oxalato)borate, [P6,6,6,14][BOB]; along with [BOB]-, a metastable transition anionic complex (TAC) of dihydroxy(oxalato)borate with oxalic acid, [B(C2O4)(OH)2·(HOOC-COOH)]-, was also formed and passed into the ionic liquid in the course of the metathesis reaction with trihexyl(tetradecyl)phosphonium chloride. On the contrary, Na[BOB] was found to be a more suitable reagent for the synthesis of this IL, because [BOB]- anions safely passed into the final IL without hydrolysis, when metathesis reactions were performed using aqueous-free media. Since ultra-pure Na[BOB] is not commercially available, in this work, a preparation protocol for ultra-pure (>99%) Na[BOB] was developed: (i) molar ratios of boric and oxalic acids were optimised to minimise boron-containing impurities, (ii) the Na[BOB] product was thoroughly purified by sequential washing of a fine powder product in hot acetonitrile and ethanol and (iii) characterised using powder X-ray diffraction and solid-state 11B MAS NMR spectroscopy. The physico-chemical properties of the prepared boron-impurity-free IL, i.e., its density, viscosity, electric conductivity, glass-transition temperature and thermal stability, were found to be significantly different from those of the previously reported [P6,6,6,14][BOB], containing ca. 45 mol% of TAC, [B(C2O4)(OH)2·(HOOC-COOH)]-. It was found that a high-purity [P6,6,6,14][BOB] prepared in this work has a considerably lower viscosity, a higher viscosity index and a wider electro-chemical window (ECW) compared to those of the sample of [P6,6,6,14][BOB] with ca. 45 mol% of TAC. Interestingly, [B(C2O4)(OH)2·(HOOC-COOH)]- in the latter sample almost completely transformed into [BOB]- anions upon heating of the IL sample at 413 K for 1 hour, as confirmed using both 11B and 13C NMR. Therefore, in this work, apart from a well-optimised synthetic protocol for boron-impurity-free [P6,6,6,14][BOB], implications of boron-containing transition anionic complexes in tetraalkylphosphonium-orthoborate ILs used in different applications were highlighted.

Electroresponsive structuring and friction of a non-halogenated ionic liquid in a polar solvent: effect of concentration.

Neutron reflectivity (NR) measurements have been employed to study the interfacial structuring and composition of electroresponsive boundary layers formed by an ionic liquid (IL) lubricant at an electrified gold interface when dispersed in a polar solvent. The results reveal that both the composition and extent of the IL boundary layers intricately depend on the bulk IL concentration and the applied surface potential. At the lowest concentration (5% w/w), a preferential adsorption of the IL cation at the gold electrode is observed, which hinders the ability to electro-induce changes in the boundary layers. In contrast, at higher IL bulk concentrations (10 and 20% w/w), the NR results reveal a significantly larger concentration of the IL ions at the gold interface that exhibit significantly greater electroresponsivity, with clear changes in the layer composition and layer thickness observed for different potentials. In complementary atomic force microscopy (AFM) measurements on an electrified gold surface, such IL boundary layers are demonstrated to provide excellent friction reduction and electroactive friction (known as tribotronics). In agreement with the NR results obtained, clear concentration effects are also observed. Together such results provide valuable molecular insight into the electroactive structuring of ILs in solvent mixtures, as well as provide mechanistic understanding of their tribotronic behaviours.

Effect of water on the electroresponsive structuring and friction in dilute and concentrated ionic liquid lubricant mixtures.

The effect of water on the electroactive structuring of a tribologically relevant ionic liquid (IL) when dispersed in a polar solvent has been investigated at a gold electrode interface using neutron reflectivity (NR). For all solutions studied, the addition of small amounts of water led to clear changes in electroactive structuring of the IL at the electrode interface, which was largely determined by the bulk IL concentration. At a dilute IL concentration, the presence of water gave rise to a swollen interfacial structuring, which exhibited a greater degree of electroresponsivity with applied potential compared to an equivalent dry solution. Conversely, for a concentrated IL solution, the presence of water led to an overall thinning of the interfacial region and a crowding-like structuring, within which the composition of the inner layer IL layers varied systematically with applied potential. Complementary nanotribotronic atomic force microscopy (AFM) measurements performed for the same IL concentration, in dry and ambient conditions, show that the presence of water reduces the lubricity of the IL boundary layers. However, consistent with the observed changes in the IL layers observed by NR, reversible and systematic control of the friction coefficient with applied potential was still achievable. Combined, these measurements provide valuable insight into the implications of water on the interfacial properties of ILs at electrified interfaces, which inevitably will determine their applicability in tribotronic and electrochemical contexts.

Interfacial structuring of non-halogenated imidazolium ionic liquids at charged surfaces: effect of alkyl chain length.

Control of the interfacial structures of ionic liquids (ILs) at charged interfaces is important to many of their applications, including in energy storage solutions, sensors and advanced lubrication technologies utilising electric fields. In the case of the latter, there is an increasing demand for the study of non-halogenated ILs, as many fluorinated anions have been found to produce corrosive and toxic halides under tribological conditions. Here, the interfacial structuring of a series of four imidazolium ILs ([CnC1Im]) of varying alkyl chain lengths (n = 5, 6, 7, 10), with a non-halogenated borate-based anion ([BOB]), have been studied at charged interfaces using sum frequency generation (SFG) spectroscopy and neutron reflectivity (NR). For all alkyl chain lengths, the SFG spectra show that the cation imidazolium ring responds to the surface charge by modifying its orientation with respect to the surface normal. In addition, the combination of SFG spectra with electrochemical NR measurements reveals that the longest alkyl chain length (n = 10) forms a bilayer structure at all charged interfaces, independent of the ring orientation. These results demonstrate the tunability of IL interfacial layers through the use of surface charge, as well as effect of the cation alkyl chain length, and provide valuable insight into the charge compensation mechanisms of ILs.

Electro-Responsive Surface Composition and Kinetics of an Ionic Liquid in a Polar Oil.

The quartz crystal microbalance (QCM) has been used to study how the interfacial layer of an ionic liquid dissolved in a polar oil at low weight percentages responds to changes in applied potential. The changes in surface composition at the QCM gold surface depend on both the magnitude and sign of the applied potential. The time-resolved response indicates that the relaxation kinetics are limited by the diffusion of ions in the interfacial region and not in the bulk, since there is no concentration dependence. The measured mass changes cannot be explained only in terms of simple ion exchange; the relative molecular volumes of the ions and the density changes in response to ion exclusion must be considered. The relaxation behavior of the potential between the electrodes upon disconnecting the applied potential is more complex than that observed for pure ionic liquids, but a measure of the surface charge can be extracted from the exponential decay when the rapid initial potential drop is accounted for. The adsorbed film at the gold surface consists predominantly of ionic liquid despite the low concentration, which is unsurprising given the surtactant-like structures of (some of) the ionic liquid ions. Changes in response to potential correspond to changes in the relative numbers of cations and anions, rather than a change in the oil composition. No evidence for an electric field induced change in viscosity is observed. This work shows conclusively that electric potentials can be used to control the surface composition, even in an oil-based system, and paves the way for other ion solvent studies.

Rheology of phosphonium ionic liquids: a molecular dynamics and experimental study.

We have studied the rheological behavior of the ionic liquid trihexyl(tetradecyl)phosphonium bis(mandelato)borate, [P66614][BMB], and compared it with that of another ionic liquid, namely trihexyl(tetradecyl)phosphonium chloride, [P66614][Cl]. The non-halogenated [P66614][BMB] has been selected as it is known to provide enhanced lubrication performance and is, consequently, of technological importance. The ionic liquid [P66614][Cl], despite its relatively simple anion, exhibits viscosities very similar to those of [P66614][BMB], making it an excellent reference fluid for the modeling study. The viscosities of the ionic liquids have been obtained by equilibrium atomistic simulations using the Green-Kubo relation, and by performing nonequilibrium shear flow simulations. The influence of the simulation system size and a reduction of the atomic charges on the viscosities of the ionic liquids are systematically studied. The atomic charges are reduced to mimic the temperature dependent charge transfer and polarization effects. It has been found that scaling the point charges with factors between 0.60 and 0.80 from full ion charges can provide reliable viscosities of [P66614][BMB], consistent with the experimentally measured viscosities within the studied temperature interval from 373 to 463 K. The viscosities of [P66614][Cl] have been obtained with scaling factors between 0.80 and 1.0 reflecting the lower polarizability and charge transfer effects of the chloride anion.

Electro-responsivity of ionic liquid boundary layers in a polar solvent revealed by neutron reflectance.

Using neutron reflectivity, the electro-responsive structuring of the non-halogenated ionic liquid (IL) trihexyl(tetradecyl)phosphonium-bis(mandelato)borate, [P6,6,6,14][BMB], has been studied at a gold electrode surface in a polar solvent. For a 20% w/w IL mixture, contrast matched to the gold surface, distinct Kiessig fringes were observed for all potentials studied, indicative of a boundary layer of different composition to that of the bulk IL-solvent mixture. With applied potential, the amplitudes of the fringes from the gold-boundary layer interface varied systematically. These changes are attributable to the differing ratios of cations and anions in the boundary layer, leading to a greater or diminished contrast with the gold electrode, depending on the individual ion scattering length densities. Such electro-responsive changes were also evident in the reflectivities measured for the pure IL and a less concentrated (5% w/w) IL-solvent mixture at the same applied potentials, but gave rise to less pronounced changes. These measurements, therefore, demonstrate the enhanced sensitivity achieved by contrast matching the bulk solution and that the structure of the IL boundary layers formed in mixtures is strongly influenced by the bulk concentration. Together these results represent an important step in characterising IL boundary layers in IL-solvent mixtures and provide clear evidence of electro-responsive structuring of IL ions in their solutions with applied potential.

Acceleration of diffusion in ethylammonium nitrate ionic liquid confined between parallel glass plates.

Diffusion of EAN confined between polar glass plates separated by a few micrometers is higher by a factor of ca. 2 as compared to bulk values. Formation of a new phase, different to the bulk, was suggested.

Influence of electric potential on the apparent viscosity of an ionic liquid: facts and artifacts.

According to recent findings, the steady shear viscosity of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][Tf2N]) decreases significantly under the influence of electric potential. This implies a causal connection between nanoscale ordering at the electrified interface and a macroscopic change of transport properties. To study this phenomenon in more detail, we reproduced the above-mentioned measurements; however, we find no evidence that the viscosity of [Emim][Tf2N] is a function of electric potential. Additionally, our results show that steady shear measurements can lead to artifacts that, at first glance, may appear to be potential-induced changes in viscosity. We demonstrate that the artifacts result from a sliding electrical contact at the working electrode of the electrochemical cell and we suggest to consider our findings for future viscosity measurements of ionic liquids.

Self-diffusion and interactions in mixtures of imidazolium bis(mandelato)borate ionic liquids with polyethylene glycol: (1) H NMR study.

We used (1) H nuclear magnetic resonance pulsed-field gradient to study the self-diffusion of polyethylene glycol (PEG) and ions in a mixture of PEG and imidazolium bis(mandelato)borate ionic liquids (ILs) at IL concentrations from 0 to 10 wt% and temperatures from 295 to 370 K. PEG behaves as a solvent for these ILs, allowing observation of separate lines in (1) H NMR spectra assigned to the cation and anion as well as to PEG. The diffusion coefficients of PEG, as well as the imidazolium cation and bis(mandelato)borate (BMB) anion, differ under all experimental conditions tested. This demonstrates that the IL in the mixture is present in at least a partially dissociated state, while the lifetimes of the associated states of the ions and ions with PEG are less than ~30 ms. Generally, increasing the concentration of the IL leads to a decrease in the diffusion coefficients of PEG and both ions. The diffusion coefficient of the anion is less than that of the cation; the molecular mass dependence of diffusion of ions can be described by the Stokes-Einstein model. NMR chemical shift alteration analysis showed that the presence of PEG changes mainly the chemical shifts of protons belonging to imidazole ring of the cation, while chemical shifts of protons of anions and PEG remain unchanged. This demonstrated that the imidazolium cation interacts mainly with PEG, which most probably occurs through the oxygen of PEG and the imidazole ring. The BMB anion does not strongly interact with PEG, but it may be indirectly affected by PEG through interaction with the cation, which directly interacts with PEG.

The effect of the cation alkyl chain length on density and diffusion in dialkylpyrrolidinium bis(mandelato)borate ionic liquids.

The physicochemical properties of ionic liquids are strongly affected by the selective combination of the cations and anions comprising the ionic liquid. In particular, the length of the alkyl chains of ions has a clear influence on the ionic liquid's performance. In this paper, we study the self-diffusion of ions in a series of halogen-free boron-based ionic liquids (hf-BILs) containing bis(mandelato)borate anions and dialkylpyrrolidinium cations with long alkyl chains CnH2n+1 with n from 4 to 14 within a temperature range of 293-373 K. It was found that the hf-BILs with n = 4-7 have very similar diffusion coefficients, while hf-BILs with n = 10-14 exhibit two liquid sub-phases in almost the entire temperature range studied (293-353 K). Both liquid sub-phases differ in their diffusion coefficients, while values of the slower diffusion coefficients are close to those of hf-BILs with shorter alkyl chains. To explain the particular dependence of diffusion on the alkyl chain length, we examined the densities of the hf-BILs studied here. It was shown that the dependence of the density on the number of CH2 groups in long alkyl chains of cations can be accurately described using a "mosaic type" model, where regions of long alkyl chains of cations (named 'aliphatic' regions) and the residual chemical moieties in both cations and anions (named 'ionic' regions) give additive contributions. Changes in density due to an increase in temperature and the number of CH2 groups in the long alkyl chains of cations are determined predominantly by changes in the free volume of the 'ionic' regions, while 'aliphatic' regions are already highly compressed by van der Waals forces, which results in only infinitesimal changes in their free volumes with temperature.

Small-Angle Neutron Scattering Insights into 2-Ethylhexyl Laurate: A Remarkable Bioester.

Commercial (protiated) samples of the "green" and biodegradable bioester 2-ethylhexyl laurate (2-EHL) were mixed with D-2-EHL synthesized by hydrothermal deuteration, with the mixtures demonstrating bulk structuring in small-angle neutron scattering measurements. Analysis in a polymer scattering framework yielded a radius of gyration (Rg) of 6.5 Å and a Kuhn length (alternatively described as the persistence length or average segment length) of 11.2 Å. Samples of 2-EHL dispersed in acetonitrile formed self-assembled structures exceeding the molecular dimensions of the 2-EHL, with a mean aggregation number (Nagg) of 3.5 ± 0.2 molecules across the tested concentrations. We therefore present structural evidence that this ester can function as a nonionic (co)surfactant. The available surfactant-like conformations appear to enable performance beyond the low calculated hydrophilic-lipophilic balance value of 2.9. Overall, our data offer an explanation for 2-EHL's interfacial adsorption properties via self-assembly, resulting in strong emolliency and lubricity for this sustainable ester-based bio-oil.

Anion Architecture Controls Structure and Electroresponsivity of Anhalogenous Ionic Liquids in a Sustainable Fluid.

Three nonhalogenated ionic liquids (ILs) dissolved in 2-ethylhexyl laurate (2-EHL), a biodegradable oil, are investigated in terms of their bulk and electro-interfacial nanoscale structures using small-angle neutron scattering (SANS) and neutron reflectivity (NR). The ILs share the same trihexyl(tetradecyl)phosphonium ([P6,6,6,14]+) cation paired with different anions, bis(mandelato)borate ([BMB]-), bis(oxalato)borate ([BOB]-), and bis(salicylato)borate ([BScB]-). SANS shows a high aspect ratio tubular self-assembly structure characterized by an IL core of alternating cations and anions with a 2-EHL-rich shell or corona in the bulk, the geometry of which depends upon the anion structure and concentration. NR also reveals a solvent-rich interfacial corona layer. Their electro-responsive behavior, pertaining to the structuring and composition of the interfacial layers, is also influenced by the anion identity. [P6,6,6,14][BOB] exhibits distinct electroresponsiveness to applied potentials, suggesting an ion exchange behavior from cation-dominated to anion-rich. Conversely, [P6,6,6,14][BMB] and [P6,6,6,14][BScB] demonstrate minimal electroresponses across all studied potentials, related to their different dissociative and diffusive behavior. A mixed system is dominated by the least soluble IL but exhibits an increase in disorder. This work reveals the subtlety of anion architecture in tuning bulk and electro-interfacial properties, offering valuable molecular insights for deploying nonhalogenated ILs as additives in biodegradable lubricants and supercapacitors.

NMR self-diffusion study of a phosphonium bis(mandelato)borate ionic liquid.

Newly synthesised halogen-free boron based ionic liquids (hf-BILs) composed of chelated orthoborate anions and phosphonium cations have hydrolytic stability, low melting point and outstanding wear and friction reducing properties. We report here the peculiarities of self-diffusion in one representative from this class, trihexyltetradecylphosphonium bis(mandelato)borate, [P6,6,6,14][BMB], in the temperature range of its practical interest, 20-100 °C. NMR techniques demonstrated complicated diffusional behaviour - the ionic liquid can exist in one or two liquid "phases". In the low-temperature range (20-50 °C), two phases coexist where the cations, [P6,6,6,14], are contained mainly in the phase with slower diffusion coefficients while the anions, [BMB], are in the phase with faster diffusion coefficients. Cations have lower diffusion coefficients with a factor of 20 as compared with the anions, an effect which is caused by aggregation of cations into domains due to so-called "hydrophobic interaction" of their hydrocarbon chains. As the temperature rises above 60 °C, the two phases merge into one where both ions have equal diffusion coefficients. This is caused by thermal motion making the cation domains smaller in size and more easily interacting with anions. As a result, anions and cations diffuse in this high-temperature range as a pair.

Tuneable interphase transitions in ionic liquid/carrier systems via voltage control.

The structure and interaction of ionic liquids (ILs) influence their interfacial composition, and their arrangement (i.e., electric double-layer (EDL) structure), can be controlled by an electric field. Here, we employed a quartz crystal microbalance (QCM) to study the electrical response of two non-halogenated phosphonium orthoborate ILs, dissolved in a polar solvent at the interface. The response is influenced by the applied voltage, the structure of the ions, and the solvent polarizability. One IL showed anomalous electro-responsivity, suggesting a self-assembly bilayer structure of the IL cation at the gold interface, which transitions to a typical EDL structure at higher positive potential. Neutron reflectivity (NR) confirmed this interfacial structuring and compositional changes at the electrified gold surface. A cation-dominated self-assembly structure is observed for negative and neutral voltages, which abruptly transitions to an anion-rich interfacial layer at positive voltages. An interphase transition explains the electro-responsive behaviour of self-assembling IL/carrier systems, pertinent for ILs in advanced tribological and electrochemical contexts.

Tribotronic control of an ionic boundary layer in operando extends the limits of lubrication.

The effect of electric potential on the lubrication of a non-halogenated phosphonium orthoborate ionic liquid used as an additive in a biodegradable oil was studied. An in-house tribotronic system was built around an instrument designed to measure lubricant film thickness between a rolling steel ball and a rotating silica-coated glass disc. The application of an electric field between the steel ball and a set of customized counter-electrodes clearly induced changes in the thickness of the lubricant film: a marked decrease at negative potentials and an increase at positive potentials. Complementary neutron reflectivity studies demonstrated the intrinsic electroresponsivity of the adsorbate: this was performed on a gold-coated silicon block and made possible in the same lubricant system by deuterating the oil. The results indicate that the anions, acting as anchors for the adsorbed film on the steel surface, are instrumental in the formation of thick and robust lubricating ionic boundary films. The application of a high positive potential, outside the electrochemical window, resulted in an enormous boost to film thickness, implicating the formation of ionic multi-layers and demonstrating the plausibility of remote control of failing contacts in inaccessible machinery, such as offshore wind and wave power installations.

Novel halogen-free chelated orthoborate-phosphonium ionic liquids: synthesis and tribophysical properties.

We report on the synthesis, characterisation, and physical and tribological properties of halogen-free ionic liquids based on various chelated orthoborate anions with different phosphonium cations, both without halogen atoms in their structure. Important physical properties of the ILs including glass transition temperatures, density, viscosity and ionic conductivity were measured and are reported here. All of these new halogen-free orthoborate ionic liquids (hf-BILs) are hydrophobic and hydrolytically stable liquids at room temperature. As lubricants, these hf-BILs exhibit considerably better antiwear and friction reducing properties under boundary lubrication conditions for steel-aluminium contacts as compared with fully formulated (15W-50 grade) engine oil. Being halogen free these hf-BILs offer a more environmentally benign alternative to ILs being currently developed for lubricant applications.

The effect of anion architecture on the lubrication chemistry of phosphonium orthoborate ionic liquids.

Phosphonium ionic liquids with orthoborate anions have been studied in terms of their interfacial film formation, both physisorbed and sacrificial from chemical breakdown, in sheared contacts of varying harshness. The halogen-free anion architecture was varied through (i) the heteronuclear ring size, (ii) the hybridisation of the constituent atoms, and (iii) the addition of aryl functionalities. Time of Flight-Secondary Ion Mass Spectrometry analysis revealed the extent of sacrificial tribofilm formation allowing the relative stability of the ionic liquids under tribological conditions to be determined and their breakdown mechanisms to be compared to simple thermal decomposition. Overall, ionic liquids outperformed reference oils as lubricants; in some cases, sacrificial films were formed (with anion breakdown a necessary precursor to phosphonium cation decomposition) while in other cases, a protective, self-assembly lubricant layer or hybrid film was formed. The salicylate-based anion was the most chemically stable and decomposed only slightly even under the harshest conditions. It was further found that surface topography influenced the degree of breakdown through enhanced material transport and replenishment. This work thus unveils the relationship between ionic liquid composition and structure, and the ensuing inter- and intra-molecular interactions and chemical stability, and demonstrates the intrinsic tuneability of an ionic liquid lubrication technology.

Diffusion of Ions in Phosphonium Orthoborate Ionic Liquids Studied by 1H and 11B Pulsed Field Gradient NMR.

Non-halogenated boron-based ionic liquids (ILs) composed of phosphonium cations and chelated orthoborate anions have high hydrolytic stability, low melting point and exceptional properties for various applications. This study is focused on ILs with the same type of cation, trihexyltetradecylphosphonium ([P6,6,6,14]+), and two orthoborate anions, such as bis(salicylato)borate ([BScB]-) and bis(oxalato)borate ([BOB]-). We compare the results of this study with our previous studies on ILs with bis(mandelato)borate ([BMB]-) and a variety of different cations (tetraalkylphosphonium, dialkylpyrrolidinium and dialkylimidazolium). The ion dynamics and phase behavior of these ILs is studied using 1H and 11B pulsed-field-gradient (PFG) NMR. PFG NMR is demonstrated to be a useful tool to elucidate the dynamics of ions in this class of phosphonium orthoborate ILs. In particular, the applicability of 11B PFG NMR for studying anions without 1H, such as [BOB]-, and the limitations of this technique to measure self-diffusion of ions in ILs are demonstrated and discussed in detail for the first time.