Selective Gas Adsorption in the Flexible Metal-Organic Frameworks Cu(BDTri)L (L = DMF, DEF)

Use of the ditopic ligand 1,4-benzenedi(1H-1,2,3-triazole) (H(2)BDTri) enabled isolation of two new three-dimensional metal-organic frameworks of formulae Cu(BDTri)L in which L = DMF (1) and diethylformamide (DEF; 2). These compounds have the same primary structure, featuring one-dimensional channels with the bridging DMF or DEF molecules pointing into the cavity. Upon exposure to solvent vapors, both display a reversible flexibility, as characterized by single-crystal to single-crystal phase transitions in 1. The O-2 adsorption isotherms for the compounds show a two-step adsorption behavior associated with a permanent microporosity and a pore-opening process. In the case of N-2 adsorption, only 1 exhibits a two-step adsorption isotherm, whereas 2 does not present any pore opening, demonstrating that design of a flexible framework cavity can control the pore opening and thereby possibly enhance O-2/N-2 separation.