Photoinduced Electron‐Transfer (PIET) Strategy for Selective Adsorption of CO2 over C2H2 in a MOF

Similarities in sizes, shapes, and physical properties between carbon dioxide (CO2) and acetylene (C2H2) make it a great challenge to separate the major impurity CO2 from products in C2H2 production. The use of porous materials is an appealing path to replace current very costly and energy‐consuming technologies, such as solvent extraction and cryogenic distillation; however, high CO2/C2H2 uptake ratio with minor adsorption of C2H2 at standard pressure was only unexpectedly observed in scarce examples in recent years although the related research started early at 1950s, and general design strategies to realize this aim are still absent. This work has successfully developed an efficient PIET strategy and obtained the second highest CO2/C2H2 adsorption ratio for porous materials in a proof‐of‐concept MOF with a photochromism‐active bipyridinium zwitterion. An unprecedented photocontrollable gate effect, owing to change of interannular dihedral after photoinduced generation of radical species, was also observed for the first time. These findings will inspire design and synthesis of porous materials for high efficient gas adsorption and separation. Using porous materials is a promising technique but a great challenge to achieve high CO2/C2H2 uptake ratio. This work has developed a PIET strategy and obtained the second highest CO2/C2H2 adsorption ratio for porous materials. These findings will promote the development of a new generation of CO2‐selective adsorption technique in C2H2 production and inspire design and synthesis of porous materials for high efficient gas adsorption and separation.