Are nature's strategies the solutions to the rational design of low-melting, lipophilic ionic liquids?

Abstract

Ionic liquids (ILs) have emerged as a new class of materials, displaying a unique capability to self-assemble into micelles, liposomes, liquid crystals, and microemulsions. Despite evident interest, advancements in the controlled formation of amphiphilic ILs remain in the early stages. Taking inspiration from nature, we introduced the concept of lipid-like (or lipid-inspired) ILs more than a decade ago, aiming to create very low-melting, highly lipophilic ILs that are potentially bio-innocuous - a combination of attributes that is frequently antithetical but highly desirable from several application-specific standpoints. Lipid-like ILs are a subclass of functional organic liquid salts that include a range of lipidic side chains such as saturated, unsaturated, linear, branched, and thioether while retaining melting points below room temperature. It was observed in several homologous series of [Cnmim] ILs that elongation of N-appended alkyl chains to greater than seven carbons leads to a substantial increase in melting point (Tm) - which is the most characteristic feature of ILs. Accordingly, it is challenging to develop ILs with low Tm values while preserving their hydrophobicity and self-organizing properties. We found that two alternative Tm depressive approaches are useful. One of these is the replacement of the double bonds with thioether moieties in the alkyl chains, as detailed in several published papers detailing the chemistry of these ILs. Employing thiol-ene and thiol-yne click reactions is a facile, robust, and orthogonal method to overcome the challenges associated with the synthesis of alkyl thioether-functionalized ILs. The second approach involves replacing the double bonds with the cisoid cyclopropyl motif, mimicking the strategy used by certain organisms to modulate cell membrane fluidity. This discovery has the potential to greatly impact the utilization of lipid-like ILs in various applications, including gene delivery, lubricants, heat transfer fluids, and haloalkane separations, among others. This feature article presents a concise, historical overview, highlighting key findings from our work while offering speculation about the future trajectory of this de novo class of soft organic-ion materials.