Crystalline Porous Organic Frameworks Based on Multiple Dynamic Linkages

Abstract

A novel class of crystalline porous materials has been developed utilizing multilevel dynamic linkages, including covalent B‐O, dative B←N and hydrogen bonds. Typically, boronic acids undergo in situ condensation to afford B3O3‐based units, which further extend to molecular complexes or chains via B←N bonds. The obtained superstructures are subsequently interconnected via hydrogen bonds and π‐π interactions, producing crystalline porous organic frameworks (CPOFs). The CPOFs display excellent solution processability, allowing dissolution and subsequent crystallization to their original structures, independent of recrystallization conditions, possibly due to the diverse bond energies of the involved interactions. Significantly, the CPOFs can be synthesized on a gram‐scale using cost‐effective monomers. In addition, the numerous acidic sites endow the CPOFs with high NH3 capacity, surpassing most porous organic materials and commercial materials.