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.