Diffusion-rate sieving of propylene and propane mixtures in a cooperatively dynamic porous crystal.

Selective molecular recognition is an important alternative to the energy-intensive industrial separation process. Porous coordination polymers (PCPs) offer designing platforms for gas separation because they possess precise controllability over structures at the molecular level. However, PCPs-based gas separations are dominantly achieved using strong adsorptive sites for thermodynamic recognition or pore-aperture control for size sieving, which suffer from insufficient selectivity or sluggish kinetics. Developing PCPs that work at high temperatures and feature both high uptake capacity and selectivity is urgently required but remains challenging. Herein, we report diffusion-rate sieving of propylene/propane (CH/CH) at 300 K by constructing a PCP material whose global and local dynamics cooperatively govern the adsorption process via the mechanisms of the gate opening for CH and the diffusion regulation for CH, respectively, yielding substantial differences in both uptake capacity and adsorption kinetics. Dynamic separation of an equimolar CH/CH mixture reveals outstanding sieving performance with a CH purity of 99.7% and a separation factor of 318.