A partially fluorinated, angular tetracarboxylic acid linker (H4L) incorporating a pendant amine moiety forms a three-dimensional. Zn(II) framework, 1. The structure consists of paddle-wheel Zn-2(CO2)(4) secondary building units (SBUs) and Zni(2)(CO2)(24) supramolecular building blocks (SBBs). Thermal stability of 1(Cu) is found to be low. However, it undergoes transmetalation reaction with Cu(II) at room temperature without losing crystallinity affording an isostructural framework, 1(Cu). Framework 1(Cu). is thermally robust and allows generation of the solvent-free porous framework 1(Cu)' upon activation with coordinatively unsaturated metal centers. Framework 1(Cu)' exhibits water stability and at 77 K, adsorbs 2.56 wt % of H-2 up to 1 bar that significantly increases to 4.01 wt % at 13 bar. Also, this framework gives a high adsorption of 164.70 cc/g of CH4 (11.7 wt %) at 303 K and 60 bar. The channel surfaces decorated with -NH2 group and unsaturated metal centers in 1(Cu)' allow a promising 36.4 wt % of CO, adsorption at 1 bar and 273 K. Moreover, it exhibits pronounced selectivity of CO2 adsorption over N-2 and H-2 at 273 K. Finally, the versatility of 1(Cu)' is shown by its excellent heterogeneous catalytic activity in the Biginelli coupling reactions involving an aldehyde, urea, and ethylacetoacetate to afford dihydroprimidinones.