Isoreticular Contraction of Cage-like Metal-Organic Frameworks with Optimized Pore Space for Enhanced C 2 H 2 /CO 2 and C 2 H 2 /C 2 H 4 Separations.

The C 2 H 2 separation from CO 2 and C 2 H 4 is of great importance yet highly challenging in the petrochemical industry, owing to their similar physical and chemical properties. Herein, the pore nanospace engineering of cage-like mixed-ligand MFOF-1 has been accomplished via contracting the size of the pyridine- and carboxylic acid-functionalized linkers and introducing a fluoride- and sulfate-bridging cobalt cluster, based on a reticular chemistry strategy. Compared with the prototypical MFOF-1, the constructed FJUT-1 with the same topology presents significantly improved C 2 H 2 adsorption capacity, and selective C 2 H 2 separation performance due to the reduced cage cavity size, functionalized pore surface, and appropriate pore volume. The introduction of fluoride- and sulfate-bridging cubane-type tetranuclear cobalt clusters bestows FJUT-1 with exceptional chemical stability under harsh conditions while providing multiple potential C 2 H 2 binding sites, thus rendering the adequate ability for practical C 2 H 2 separation application as confirmed by the dynamic breakthrough experiments under dry and humid conditions. Additionally, the distinct binding mechanism is suggested by theoretical calculations in which the multiple supramolecular interactions involving C-H···O, C-H···F, and other van der Waals forces play a critical role in the selective C 2 H 2 separation.