Complete Series of Monohalogenated Isoreticular Metal-Organic Frameworks: Synthesis and the Importance of Activation Method

A series of four IRMOFs with -F, -Cl, -Br, and -I terephthalate linkers was synthesized and characterized with respect to crystal structure, surface area, and nitrogen gas sorption. The activation of these materials was systematically evaluated, using several solvent-exchange methods and supercritical CO(2) drying. The results demonstrate a strong dependence of surface area on the activation method used. Materials with surface areas comparable to predicted values were achieved, considerably improving upon previously reported values for IRMOF-2 and its -I variant. Finally, ambient-temperature nitrogen adsorption isotherms were measured. These data clearly demonstrate that the adsorption of a weakly interacting gas can be improved by increasing linker polarizability, confirming previous speculation in the literature.