Metal-organic frameworks constructed from crown ether-based 1,4-benzenedicarboxylic acid derivatives

A series of unprecedented crown ether- and thiacrown ether-derivatized benzene dicarboxylic acid (H₂bdc) ligands has been synthesized and incorporated into the prototypical isoreticular metal-organic framework (IRMOF) and UiO-66 materials. In the case of UiO-66, only MOFs comprised from a mixed-ligand composition, requiring both unsubstituted bdc and crown ether containing ligands, could be prepared. These are among the few ligand derivatives, and resulting MOFs, that incorporate a macrocyclic group directly on the bdc ligand, providing a new, modular platform for exploring new supramolecular and coordination chemistry within MOFs.