Amine‐Tagged Fragmented Ligand Installation for Covalent Modification of MOF‐74

Abstract MOF‐74 is one of the most explored metal–organic frameworks (MOFs), but its functionalization is limited to the dative post‐synthetic modification (PSM) of the monodentate solvent site. Owing to the nature of the organic ligand and framework structure of MOF‐74, the covalent PSM of MOF‐74 is very demanding. Herein, we report, for the first time, the covalent PSM of amine‐tagged defective Ni‐MOF‐74, which is prepared by de novo solvothermal synthesis by using aminosalicylic acid as a functionalized fragmented organic ligand. The covalent PSM of the amino group generates metal binding sites, and subsequent post‐synthetic metalation with Pd II ions affords the Pd II ‐incorporated Ni‐MOF‐74 catalyst. This catalyst exhibits highly efficient, size‐selective, and recyclable catalytic activity for the Suzuki–Miyaura cross‐coupling reaction. This strategy is also useful for the covalent modification of amine‐tagged defective Ni 2 (DOBPDC), an expanded analogue of MOF‐74.