Topology-Directed Cage Engineering in MOFs for Efficient C₂H₂/CO₂/C₂H₄ Separation

Cage-based porous materials, leveraging their unique "confined windows-expanded cavities" synergistic architecture, have demonstrated remarkable advantages in the field of gas adsorption and separation. This study presents a topology-directed in situ assembly strategy that successfully constructs metal-organic frameworks with tailored pore structures. Using the distinctive cage-channel <b>soc</b> topological frameworks as a template, by innovatively reversing the roles of traditional nodes and linkers, we employed the conformationally flexible hexa-pyridine ligands as six-connected nodes and utilized undercoordinated Cu²⁺ as five-connected linkers, in combination with halogen anions (F^-, Cl^-, and Br^-) as two-connected topological "blockers", resulting in the successful synthesis of three MOF materials (<b>LNU-H1</b>, <b>LNU-H2</b>, and <b>LNU-H3</b>) featuring an unprecedented <b>jcq</b> topological network. These materials exhibit a unique "confined window-expanded cavity" synergistic structure, achieving complete closure of linear channels. Notably, <b>LNU-H1</b> demonstrated exceptional performance in the separation of ternary C₂H₂/CO₂/C₂H₄ gas mixtures, as validated by dynamic breakthrough experiments under industrially relevant conditions. This study not only confirms the effectiveness of the topology-directed pore engineering approach but also provides new insights into the development of advanced, energy-efficient functional materials for gas separation applications.