Perfluoroalkane Functionalization of NU-1000 via Solvent-Assisted Ligand Incorporation: Synthesis and CO2 Adsorption Studies

A new functionalization technique, solvent-assisted ligand incorporation (SALI), was developed to efficiently incorporate carboxylate-based functionalities in the Zr-based metal–organic framework, NU-1000. Unlike previous metal node functionalization strategies, which utilize dative bonding to coordinatively unsaturated metal sites, SALI introduces functional groups as charge compensating and strongly bound moieties to the Zr6 node. Utilizing SALI, we have efficiently attached perfluoro­alkane carboxylates of various chain lengths (C1–C9) on the Zr6 nodes of NU-1000. These fluoro­alkane-functionalized mesoporous MOFs, termed herein SALI-n, were studied experimentally and theoretically as potential CO2 capture materials.