Entropy-Driven Porous Liquids Allowing Gas Solubility in Solvent-Filled Imine-Based Porous Organic Cages

Porous liquids offer a promising platform for gas separation by combining fluid processability with intrinsic molecular porosity. Traditional Type II porous liquids are formed by dissolving porous molecular cages in size-excluded solvents, limiting solvent options and practical applications. In this work, we introduce a novel method of creating Type II porous liquids using common small solvents, where intrinsic porosity is achieved at elevated pressures due to the selective displacement of solvent molecules by gas molecules within the cage structures. Using molecular simulations, we investigate the behavior of CO₂ in solutions of the imine-based porous organic cage CC13 dissolved in small molecular solvents such as chloroform and 1,2-dimethoxyethane (DME). Grand canonical Monte Carlo simulations of solid-state CC13 reveal that selectivity reversal, where smaller CO₂ molecules displace larger solvent molecules inside the cage, is achievable at sufficiently high pressures. Temperature quench molecular dynamics simulations confirm that while CO₂ displacement within chloroform-filled cages is limited, DME enables entropy-driven cage CO₂ occupancy at pressures as low as ∼23 bar, setting up the foundation of an alternative way of forming Type II porous liquids.