While ionic liquids have proved to be versatile materials for a wide spectrum of applications, e.g., energy, materials, and medicine, several challenges remain concerning the rational design of novel materials. In light of this, a series of four triphenylphosphonium-based ionic liquids have been synthesized for the first time. These compounds exhibit high thermal stability with decomposition temperatures up to 450 °C. Their solid-state structures are characterized by single-crystal X-ray diffraction and the intermolecular interactions rigorously analyzed via Hirshfeld surface analysis. It was found that the unique geometries of the anions used in the study form distinct interactions with the cations. The interactions in the crystalline state are correlated with the thermal properties of the four ionic liquids to rationalize the melting points and phase transitions for each compound. The observed arrangements of the alkyl chains on the cations are investigated computationally to gain an understanding of how rotational freedom may impact the thermal properties of the compounds. By intention, each IL reported in this work offers a unique property profile and contributes to the ever-growing ionic liquid catalog.

New family of SO₂F-functionalized ionic liquids.

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 [C_nmim] ILs that elongation of N-appended alkyl chains to greater than seven carbons leads to a substantial increase in melting point (T_m) – which is the most characteristic feature of ILs. Accordingly, it is challenging to develop ILs with low T_m values while preserving their hydrophobicity and self-organizing properties. We found that two alternative T_m 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.

While machine learning and artificial intelligence offer promising avenues in the computer-aided design of materials, the complexity of these computational techniques remains a barrier for scientists outside of the specific fields of study. Leveraging decision tree models, inspired by empirical methodologies, offers a pragmatic solution to the knowledge barrier presented by artificial intelligence (AI). Herein, we present a model allowing for the qualitative prediction of melting points of ionic liquids derived from the crystallographic analysis of a series of phosphonium-based ionic liquids. By carefully tailoring the steric and electronic properties of the cations within these salts, trends in the melting points are observed, pointing toward the critical importance of π interactions to forming the solid state. Quantification of the percentage of these π interactions using modern quantum crystallographic approaches reveals a linear trend in the relationship of C-Hπ and π-π stacking interactions with melting points. These structure-property relationships are further examined by using computational studies, helping to demonstrate the inverse relationship of dipole moments and melting points for ionic liquids. The results provide valuable insights into the features and relationships that are consistent with achieving low T_m values in phosphonium salts, which were not apparent in earlier studies. The data gathered are presented in a simple decision tree format, allowing for visualization of the data and providing guidance toward developing yet unreported compounds.

A fundamental challenge underlying the design principles of ionic liquids (ILs) entails a lack of understanding into how tailored properties arise from the molecular framework of the constituent ions. Herein, we present detailed analyses of novel functional ILs containing a triarylmethyl (trityl) motif. Combining an empirically driven molecular design, thermophysical analysis, X-ray crystallography, and computational modeling, we achieved an in-depth understanding of structure-property relationships, establishing a coherent correlation with distinct trends between the thermophysical properties and functional diversity of the compound library. We observe a coherent relationship between melting (T _m) and glass transition (T _g) temperatures and the location and type of chemical modification of the cation. Furthermore, there is an inverse correlation between the simulated dipole moment and the T _m/T _g of the salts. Specifically, chlorination of the ILs both reduces and reorients the dipole moment, a key property controlling intermolecular interactions, thus allowing for control over T _m/T _g values. The observed trends are particularly apparent when comparing the phase transitions and dipole moments, allowing for the development of predictive models. Ultimately, trends in structural features and characterized properties align with established studies in physicochemical relationships for ILs, underpinning the formation and stability of these new lipophilic, low-melting salts.