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, H4 L, with a pendent amine moiety solvothermally forms two isostructural metal-organic frameworks (MOFs) LM (M=ZnII , CuII ). Framework LCu can also be obtained from LZn by post- synthetic metathesis without losing crystallinity. Compared with LZn , the LCu framework exhibits high thermal stability and allows removal of guest solvent and metal-bound water molecules to afford the highly porous, LCu '. At 77 K, LCu ' absorbs 2.57 wt % of H2 at 1 bar, which increases significantly to 4.67 wt % at 36 bar. The framework absorbs substantially high amounts of methane (238.38 cm3  g-1 , 17.03 wt %) at 303 K and 60 bar. The CH4 absorption at 303 K gives a total volumetric capacity of 166 cm3  (STP) cm-3 at 35 bar (223.25 cm3  g-1 , 15.95 wt %). Interestingly, the NH2 groups in the linker, which decorate the channel surface, allow a remarkable 39.0 wt % of CO2 to be absorbed at 1 bar and 273 K, which comes within the dominion of the most famous MOFs for CO2 absorption. Also, LCu ' shows pronounced selectivity for CO2 absorption over CH4 , N2 , and H2 at 273 K. The absorbed CO2 can be converted to value-added cyclic carbonates under relatively mild reaction conditions (20 bar, 120 °C). Finally, LCu ' 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.