Developing artificial porous systems with high molecular recognition performance is critical but very challenging to achieve selective uptake of a particular component from a mixture of many similar species, regardless of the size and affinity of these competing species. A porous platform that integrates multiple recognition mechanisms working cooperatively for highly efficient guest identification is desired. Here, we designed a flexible porous coordination polymer (PCP) and realised a corrugated channel system that cooperatively responds to only target gas molecules by taking advantage of its stereochemical shape, location of binding sites, and structural softness. The binding sites and structural deformation act synergistically, exhibiting exclusive discrimination gating (EDG) effect for selective gate-opening adsorption of CO₂ over nine similar gas molecules, including N₂, CH₄, CO, O₂, H₂, Ar, C₂H₆, and even higher-affinity gases such as C₂H₂ and C₂H₄. Combining in-situ crystallographic experiments with theoretical studies, it is clear that this unparalleled ability to decipher the CO₂ molecule is achieved through the coordination of framework dynamics, guest diffusion, and interaction energetics. Furthermore, the gas co-adsorption and breakthrough separation performance render the obtained PCP an efficient adsorbent for CO₂ capture from various gas mixtures.

Fluorinated gases (F-gases) play a vital role in the chemical industry and in the fields of air conditioning, refrigeration, health care, and organic synthesis. However, the direct emission of waste gases containing F-gases into the atmosphere contributes to greenhouse effects and generates toxic substances. Developing porous materials for the energy-efficient capture, separation, and recovery of F-gases is highly desired. Recently, as a highly designable porous adsorbents, metal–organic frameworks (MOFs) exhibit excellent selective sorption performance toward F-gases, especially for the recognition and separation of different F-gases with highly similar properties, showing their great potential in F-gases control and recovery. In this review, we discuss the capture and separation of F-gases and their azeotropic, near-azeotropic, and isomeric mixtures in various application scenarios by MOFs, specifically classify and analyze molecular interaction between F-gases and MOFs, and interpret the mechanisms underlying their high performance regarding both adsorption capacity and selectivity, providing a repertoire for future materials design. Challenges faced in the transformation research roadmap of MOFs adsorbent separation technologies toward F-gases are also discussed, and areas for future research endeavors are highlighted.