A new copper-based metal-organic framework [CuL(HO)]·5DMF·2HO (ZJNU-56) has been solvothermally synthesized using a custom-designed asymmetric rigid bent diisophthalate ligand, 5,5'-(1-amine-naphthyl-2,4-diyl) diisophthalic acid (HL), and structurally determined by single-crystal X-ray diffraction. ZJNU-56 features a three-dimensional (3D) open framework incorporating three different types of metal-organic cages and two distinct types of one-dimensional channels. With a moderate BET surface area of 1655 m g, optimized pore structure, and functional sites (open copper sites and Lewis basic amine groups) on the cage surface, ZJNU-56 after desolvation exhibits highly selectively adsorptive separation of CH and CO over CH under ambient conditions. At 298 K, the predicted IAST selectivities are 35.7-72.9 for an equimolar CH/CH gas mixture and 6.8-7.0 for an equimolar CO/CH gas mixture at pressures varying from 1 to 109 kPa, respectively, which are among the highest reported to date for copper-based MOFs.
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