Additive-Induced Supramolecular Isomerism and Enhancement of Robustness in Co(II)-Based MOFs for Efficiently Trapping Acetylene from Acetylene-Containing Mixtures.

Although supramolecular isomerism in metal-organic frameworks (MOFs) would offer a favorable platform for in-depth exploring their structure-property relationship, the design and synthesis of the isomers are still rather a challenging aspect of crystal engineering. Here, a pair of supramolecular isomers of Co(II)-based MOFs (FJU-88 and FJU-89) can be directionally fabricated by rational tuning the additives. In spite of the fact that the isomers have the similar Co3 secondary building units and organic linkers, they adopt distinct networks with acs and snw topologies, respectively, which derive from the conformational flexibility of the organic ligands. It is noteworthy that the porous structure of FJU-88 would be collapsed after removal of the solvent from the pores. But FJU-89a shows permanent porosity accompanied with unusual hierarchical micro- and mesopores and superior gas selective adsorption performance. In addition, FJU-89a can efficiently trap C2H2 from C2H2/CO2 and C2H2/CH4 mixture gases through fixed-bed dynamic breakthrough experiments.