Rational Design of Smart Metal–Organic Frameworks for Light-Modulated Gas Transport

Smart metal–organic frameworks (MOFs) are constructed by introducing stimuli-responsive functional groups into MOF platforms. Through membrane systems containing smart MOFs, external field-modulated gas transport can be achieved, which finds potential applications in chemical engineering. In this work, we design a series of Mg-MOF-74-III-based frameworks functionalized by arylazopyrazole groups. Methyleneamine chains with various lengths are attached to the photoresponsive azopyrazole moiety. Molecular dynamics simulations show that CO2 diffusion can be remarkably changed by controlling the cis-to-trans isomerization of the functional unit due to the tunable adsorbate–adsorbent and adsorbate–adsorbate interactions of the two states. With the optimal length of the functional chain, the spatial hindrance and adsorbate–adsorbent interaction exhibit a synergetic effect to maximize the stimuli-responsive kinetic separation of N2 over CO2. This work provides a promising strategy for elevating smart MOFs’ potential in gas separation.