Predicting Solubility and Size-Exclusivity Towards the Rational Design of Porous Liquid Solutions

Porous liquids are a sub-class of porous materials that combine permanent porosity, typically associated with solids, with the fluidity and fast mass-transfer capabilities of liquids, making them ideal candidates for gas storage and separation applications. One strategy to form porous liquids is the dissolution of discrete and permanently porous molecular species at relatively high concentrations in cavity-excluded solvents, thus introducing permanent porosity into the liquid in which it is dissolved and ensuring a solution of reasonable porosity is obtained. To access high-performance porous liquids for target applications, the selection of both the porous molecular species and the cavity-excluded solvent is key to ensuring the solvent is permanently excluded and the pore carrier is highly soluble. Finding new solvents that fit both these requirements is challenging, often resulting in a trial-and-error approach. While predictive data-driven models may be attractive, the youth of the porous liquid field currently limits the availability of data necessary to train robust models. Here, we present a computational workflow for the discovery of new porous liquid solutions combining solubility prediction software and a size-exclusivity prediction algorithm that correctly predicts size-exclusivity; this is followed by experimental validation with a representative system. Our workflow yielded size-excluded solvent and soluble porous organic cage pairs, leading to the realisation of a new porous liquid with enhanced methane uptake compared to previous systems discovered in a purely experimental high-throughput brute-force manner, highlighting the advantages of incorporating a computational workflow in the discovery of new porous liquids.