A Versatile CuII Metal–Organic Framework Exhibiting High Gas Storage Capacity with Selectivity for CO₂: Conversion of CO₂ to Cyclic Carbonate and Other Catalytic Abilities

A linear tetracarboxylic acid ligand, H 4 L, with a pendent amine moiety solvothermally forms two isostructural metal–organic frameworks (MOFs) L M (M=Zn II , Cu II ). Framework L Cu can also be obtained from L Zn by post‐ synthetic metathesis without losing crystallinity. Compared with L Zn , the L Cu framework exhibits high thermal stability and allows removal of guest solvent and metal‐bound water molecules to afford the highly porous, L Cu ′ . At 77 K, L Cu ′ absorbs 2.57 wt % of H 2 at 1 bar, which increases significantly to 4.67 wt % at 36 bar. The framework absorbs substantially high amounts of methane (238.38 cm 3 g −1 , 17.03 wt %) at 303 K and 60 bar. The CH 4 absorption at 303 K gives a total volumetric capacity of 166 cm 3 (STP) cm −3 at 35 bar (223.25 cm 3 g −1 , 15.95 wt %). Interestingly, the NH 2 groups in the linker, which decorate the channel surface, allow a remarkable 39.0 wt % of CO 2 to be absorbed at 1 bar and 273 K, which comes within the dominion of the most famous MOFs for CO 2 absorption. Also, L Cu ′ shows pronounced selectivity for CO 2 absorption over CH 4 , N 2 , and H 2 at 273 K. The absorbed CO 2 can be converted to value‐added cyclic carbonates under relatively mild reaction conditions (20 bar, 120 °C). Finally, L Cu ′ is found to be an excellent heterogeneous catalyst in regioselective 1,3‐dipolar cycloaddition reactions (“click” reactions) and provides an efficient, economic route for the one‐pot synthesis of structurally divergent propargylamines through three‐component coupling of alkynes, amines, and aldehydes.