Cyclotetrabenzoin Acetate: A Macrocyclic Porous Molecular Crystal for CO₂ Separations by Pressure Swing Adsorption**

A porous molecular crystal (PMC) assembled by macrocyclic cyclotetrabenzoin acetate is an efficient adsorbent for CO₂ separations. The 7.1×7.1 Å square pore of PMC and its ester C=O groups play important roles in improving its affinity for CO₂ molecules. The benzene walls of macrocycle engage in an apparent [π⋅⋅⋅π] interaction with the molecule of CO₂ at low pressure. In addition, the polar carbonyl groups pointing inward the square channels reduce the size of aperture to a 5.0×5.0 Å square, which offers kinetic selectivity for CO₂ capture. The PMC features water tolerance and high structural stability under vacuum and various gas adsorption conditions, which are rare among intrinsically porous organic molecules. Most importantly, the moderate adsorbate-adsorbent interaction allows the PMC to be readily regenerated, and therefore applied to pressure swing adsorption processes. The eluted N₂ and CH₄ are obtained with over 99.9 % and 99.8 % purity, respectively, and the separation performance is stable for 30 cycles. Coupled with its easy synthesis, cyclotetrabenzoin acetate is a promising adsorbent for CO₂ separations from flue and natural gases.