Gated Channels and Selectivity Tuning of CO2 over N2 Sorption by Post-Synthetic Modification of a UiO-66-Type Metal-Organic Framework.

The highly porous and stable metal-organic framework (MOF) UiO-66 was altered using post-synthetic modifications (PSMs). Prefunctionalization allowed the introduction of carbon double bonds into the framework through a four-step synthesis from 2-bromo-1,4-benzenedicarboxylic acid; the organic linker 2-allyl-1,4-benzenedicarboxylic acid was obtained. The corresponding functionalized MOF (UiO-66-allyl) served as a platform for further PSMs. From UiO-66-allyl, epoxy, dibromide, thioether, diamine, and amino alcohol functionalities were synthesized. The abilities of these compounds to adsorb CO2 and N2 were compared, which revealed the structure-selectivity correlations. All synthesized MOFs showed profound thermal stability together with an increased ability for selective CO2 uptake and molecular gate functionalities at low temperatures.