Physical and Electrochemical Analysis of N-Alkylpyrrolidinium-Substituted Boronium Ionic Liquids.

In this work, a series of novel boronium-bis(trifluoromethylsulfonyl)imide [TFSI-] ionic liquids (IL) are introduced and investigated. The boronium cations were designed with specific structural motifs that delivered improved electrochemical and physical properties, as evaluated through cyclic voltammetry, broadband dielectric spectroscopy, densitometry, thermogravimetric analysis, and differential scanning calorimetry. Boronium cations, which were appended with N-alkylpyrrolidinium substituents, exhibited superior physicochemical properties, including high conductivity, low viscosity, and electrochemical windows surpassing 6 V. Remarkably, the boronium ionic liquid functionalized with both an ethyl-substituted pyrrolidinium and trimethylamine, [(1-e-pyrr)N111BH2][TFSI], exhibited a 6.3 V window, surpassing previously published boronium-, pyrrolidinium-, and imidazolium-based IL electrolytes. Favorable physical properties and straightforward tunability make boronium ionic liquids promising candidates to replace conventional organic electrolytes for electrochemical applications requiring high voltages.

Correction: Ionic liquids of superior thermal stability. Validation of PPh4+ as an organic cation of impressive thermodynamic durability.

[This corrects the article DOI: 10.1039/D0RA03220D.].

Cyclopropane as an Unsaturation "Effect Isostere": Lowering the Melting Points in Lipid-like Ionic Liquids.

The replacement of unsaturation with a cyclopropane motif as a (bio)isostere is a widespread strategy in bacteria to tune the fluidity of lipid bilayers and protect membranes when exposed to adverse environmental conditions, e.g., high temperature, low pH, etc. Inspired by this phenomenon, we herein address the relative effect of the cyclopropanation, both cis and trans configurations, on melting points, packing efficiency, and order of a series of lipid-like ionic liquids via a combination of thermophysical analysis, X-ray crystallography, and computational modeling. The data indicate there is considerable structural latitude possible when designing highly lipophilic ionic liquids that exhibit low melting points. While cyclopropanation of the lipid-like ionic liquids provides more resistance to aerobic degradation than their olefin analogs, the impact on the melting point decrease is not as pronounced. Our results demonstrate that incorporating one or more cyclopropyl moieties in long aliphatic chains of imidazolium-based ionic liquids is highly effective in lowering the melting points of such materials relative to their counterparts bearing linear, saturated, or thioether side chains. It is shown that the cyclopropane moiety effectively disrupts packing, favoring formation of gauche conformer in the side chains, resulting in enhancement of fluidity. This was irrespective of the configuration of the methylene bridge, although marked differences in the effect of cis- and trans-monocyclopropanated ILs on the melting points were observed.

Ionic liquids of superior thermal stability. Validation of PPh4 + as an organic cation of impressive thermodynamic durability.

Recent work by Wasserscheid, et al. suggests that PPh4 + is an organic molecular ion of truly exceptional thermal stability. Herein we provide data that cements that conclusion: specifically, we show that aliphatic moieties of modified PPh4 +-based cations incorporating methyl, methylene, or methine C-H bonds burn away at high temperatures in the presence of oxygen, forming CO, CO2, and water, leaving behind the parent ion PPh4 +. The latter then undergoes no further reaction, at least below 425 °C.

Lipidic ionic liquid stationary phases for the separation of aliphatic hydrocarbons by comprehensive two-dimensional gas chromatography.

Lipidic ionic liquids (ILs) possessing long alkyl chains as well as low melting points have the potential to provide unique selectivity as well as wide operating ranges when used as stationary phases in gas chromatography. In this study, a total of eleven lipidic ILs containing various structural features (i.e., double bonds, linear thioether chains, and cyclopropanyl groups) were examined as stationary phases in comprehensive two dimensional gas chromatography (GC×GC) for the separation of nonpolar analytes in kerosene. N-alkyl-N'-methyl-imidazolium-based ILs containing different alkyl side chains were used as model structures to investigate the effects of alkyl moieties with different structural features on the selectivities and operating temperature ranges of the IL-based stationary phases. Compared to a homologous series of ILs containing saturated side chains, lipidic ILs exhibit improved selectivity toward the aliphatic hydrocarbons in kerosene. The palmitoleyl IL provided the highest selectivity compared to all other lipidic ILs as well as the commercial SUPELCOWAX 10 column. The linoleyl IL containing two double bonds within the alkyl side chain showed the lowest chromatographic selectivity. The lipidic IL possessing a cyclopropanyl group within the alkyl moiety exhibited the highest thermal stability. The Abraham solvation parameter model was used to evaluate the solvation properties of the lipidic ILs. This study provides the first comprehensive examination into the relation between lipidic IL structure and the resulting solvation characteristics. Furthermore, these results establish a basis for applying lipidic ILs as stationary phases for solute specific separations in GC×GC.

Solubility of CO2 and N2O in an Imidazolium-Based Lipidic Ionic Liquid.

Imidazolium-based ionic liquids have been extensively studied for their ability to dissolve a wide variety of gases and for their potential to be used as separation agents in industrial processes. For many short chain 1-alkyl-3-methylimidazolium bistriflimde salts, CO2 and N2O solublities are very similar. In this work, the solubility of CO2 and N2O has been measured in the lipidic ionic liquid 1-methyl-3-(Z-octadec-9-enyl)imidazolium bistriflimide ([oleyl-mim][NTf2]) at 298 K, 310 and 323 K up to ∼2 MPa. N2O was found to have higher solubility than CO2 under the same conditions, similar to the behavior observed when olive oil, a natural lipid, was the liquid solvent. However, the solubility of each gas on a mole fraction basis is lower in the ionic liquid than in olive oil. Comparison of the gas solubilities on a mass fraction basis demonstrates that CO2 solubility is nearly identical in both liquids; N2O solubility is higher than CO2 for both liquids, but more so in the olive oil. The difference is attributed to the high mass fraction of the olive oil that is lipid-like in character. The differential solubility of N2O/CO2 in this ionic liquid, in contrast to that of shorter chain 1-alkyl-3-methylimidazolium bistriflimide salts, gives physical insight into the solvent properties of this class of ionic liquids and provides further support for their lipid-like character.

Fusion and Thermal Degradation Behavior of Symmetric Sulfur-Containing Quaternary Ammonium Bromides.

Quaternary ammonium salts are widely used in consumer products and industrial processes, where their instability at elevated temperatures limits their range of applications. In this work, the thermal behavior of a new class of quaternary ammonium salts was investigated using differential scanning calorimetry. These salts contain a sulfur atom in each chain at the fourth position from the central nitrogen and are thus termed thiaquats. The temperatures at which these salts melt and thermally degrade were determined, and enthalpies and entropies of fusion were evaluated. Their melting points increase with chain lengths, in contrast to the behavior of traditional quaternary ammonium salts. Furthermore, they exhibit enthalpies and entropies of fusion significantly lower than corresponding tetraalkyl analogues. These trends provide physical insight into the molecular-level behavior of these salts, suggesting that they do not fully dissociate upon melting. The thiaquats also exhibit thermal stability to markedly higher temperatures than traditional quaternary ammonium bromides, a phenomenon that can be explained in by strong pairing between the quaternary cation and bromide anion, which inhibits possible decomposition mechanisms. This enhanced thermal stability may enable applications of these salts in processes where traditional salts are not viable, such as phase-transfer-catalyzed systems performed at elevated temperatures.

Liquid-liquid equilibria of binary mixtures of a lipidic ionic liquid with hydrocarbons.

Although structurally diverse, many ionic liquids (ILs) are polar in nature due to the strong coulombic forces inherent in ionic compounds. However, the overall polarity of the IL can be tuned by incorporating significant nonpolar content into one or more of the constituent ions. In this work, the binary liquid-liquid equilibria of one such IL, 1-methyl-3-(Z-octadec-9-enyl)imidazolium bistriflimide, with several hydrocarbons (n-hexane, n-octane, n-decane, cyclohexane, methylcyclohexane, 1-octene) is measured over the temperature range 0-70 °C at ambient pressure using a combination of cloud point and gravimetric techniques. The phase behavior of the systems are similar in that they exhibit two phases: one that is 60-90 mole% hydrocarbon and a second phase that is nearly pure hydrocarbon. Each phase exhibits a weak dependence of composition on temperature (steep curve) above ∼10 °C, likely due to swelling and restructuring of the nonpolar nano-domains of the IL being limited by energetically unfavorable restructuring in the polar nano-domains. The solubility of the n-alkanes decreases with increasing size (molar volume), a trend that continues for the cyclic alkanes, for which upper critical solution temperatures are observed below 70 °C. 1-Octene is found to be more soluble than n-octane, attributable to a combination of its lower molar volume and slightly higher polarity. The COSMO-RS model is used to predict the T-x'-x'' diagrams and gives good qualitative agreement of the observed trends. This work presents the highest known solubility of n-alkanes in an IL to date and tuning the structure of the ionic liquid to maximize the size/shape trends observed may provide the basis for enhanced separations of nonpolar species.

Crystal structure of a methimazole-based ionic liquid.

The structure of 1-methyl-2-(prop-2-en-1-ylsulfan-yl)-1H-imidazol-3-ium bromide, C7H11N2S(+)·Br(-), has monoclinic (P21/c) symmetry. In the crystal, the components are linked by N-H⋯Br and C-H⋯Br hydrogen bonds. The crystal structure of the title compound undeniably proves that methimazole reacts through the thione tautomer, rather than the thiol tautomer in this system.

The effect of the sulfur position on the melting points of lipidic 1-methyl-3-thiaalkylimidazolium ionic liquids.

A series of novel lipid-inspired ionic liquids have been synthesized employing the thiol-ene "click" reaction in a single-step process. The thermal properties were determined by differential scanning calorimetry (DSC) and showed observable trends between the C16, C18, and C20 analogues. The minimum melting points for each equivalent chain length series occur at sequential odd sulfur positions, 3, 5, and 7 for the C16, C18, and C20 series, respectively. The magnitude of melting point depression relative to the saturated homologue is observed to have a strong dependence on the position of the sulfur in the side chain. Additionally, the sulfur position corresponding to the lowest melting point for a homologous series shifts further down the chain as the chain length is increased, indicating that the maximum effect takes place near the center of the ion and not the center of the thiaalkyl chain. This synthesis provides tunability and improved thermal stability for 1-methyl-3-thiaalkylimidazolium bistriflimides and insight into structure-property relationships of lipidic ionic liquids.

On the formation of a protic ionic liquid in nature.

The practical utility of ionic liquids (ILs) makes the absence (heretofore) of reported examples from nature quite puzzling, given the facility with which nature produces many other types of exotic but utilitarian substances. In that vein, we report here the identification and characterization of a naturally occurring protic IL. It can be formed during confrontations between the ants S. invicta and N. fulva. After being sprayed with alkaloid-based S. invicta venom, N. fulva detoxifies by grooming with its own venom, formic acid. The mixture is a viscous liquid manifestly different from either of the constituents. Further, we find that the change results as a consequence of formic acid protonation of the N centers of the S. invicta venom alkaloids. The resulting mixed-cation ammonium formate milieu has properties consistent with its classification as a protic IL.

Synthesis of new lipid-inspired ionic liquids by thiol-ene chemistry: profound solvent effect on reaction pathway.

The synthesis of a series of new lipid-inspired ionic liquids through thiol-ene "click" reaction with a single-step process. This synthesis offers considerable promise as an efficient and orthogonal method to construct structurally diverse imidazolium-type ionic liquids with linear and branched cationic tails, as well as versatility in the placement of the sulfur heteroatom. Profound solvent effect in this ene reaction regioselectivity has been observed.

Ionic liquids of superior thermal stability.

In a head-to-head study, ILs based upon tetraarylphosphonium cations exhibit superior long-term thermal stability compared to familiar salts based upon imidazolium, quaternary ammonium, or tetraalkylphosphonium cations.

Structure-based tuning of T(m) in lipid-like ionic liquids. Insights from Tf2N- salts of gene transfection agents.

Ionic liquids of cations bearing two lipid-like aliphatic tails are shown to have values of T(m) that can be very low, and that can be tuned up or down by the addition, deletion, or combination of dipolar modules and side-chain double bonds.

A new building block for electroactive organic materials? Synthesis, cyclic voltammetry, single crystal X-ray structure, and DFT treatment of a unique boron-based viologen.

A boronium-based paraquat analog undergoes reductions at more negative potentials than paraquat itself, making it a promising building block for electroactive materials.

Constitutional dynamic systems of ionic and molecular liquids.

The ionic liquids N-methylpyridinium-2-carboxaldehyde Tf(2)N(-) and N-methylpyridinium-3-carboxaldehyde Tf(2)N(-) form readily-reversible covalent bonds with protic nucleophiles, creating all-liquid constitutionally dynamic materials.