Two Cu(II)-based metal-organic frameworks (MOFs) having paddle-wheel secondary building units (SBUs), namely, 1(Me) and 1(ip)(r) were synthesized solvothermally using two new bent di-isophthalate ligands incorporating different substituents. The MOFs showed high porosity (BET surface area, 2191 m(2)/g for 1(Me) and 1402 m(2)/g for For 1(Me), very high CO2 adsorption (98.5 wt % at 195 K, 42.9 wt % at 273 K, 23.3 wt % at 298 K) at 1 bar was found, while for 1(ipr) it was significantly less (14.3 wt % at 298 K and 1 bar, 54.4 wt % at 298 K at 50 bar). 1(Me) exhibited H-2 uptake of 3.2 wt % at 77 K and 1 bar of pressure, which compares well with other benchmark MOFs. For 1(Me), the H-2 uptake was found to be 2.54 wt % under similar experimental conditions. The significant adsorption of H-2 and CO2 for 1(Me) could be due to the presence of micropores as well as unsaturated metal sites in these MOFs besides the presence of substituents that interact with the gas molecules. The experimental adsorption behavior of the MOFs could be justified by theoretical calculations. Additionally, catalytic conversions of CO2 and CS2 into useful chemicals like cyclic carbonates, cyclic trithiocarbonates, and cyclic dithiocarbonates could be achieved.