Amide-linked covalent organic frameworks (amide COFs) possess enormous potentials in practical applications benefiting from their high stability and polyamide structures. However, they suffer from very limited accessibility. Herein, we report a new linkage conversion method to rapidly synthesize crystalline amide COFs through oxidation of imine linkages in their corresponding imine-linked frameworks with KHSO 5 as an oxidant under very mild conditions. This synthetic strategy is general, facile, efficient, and scalable, as demonstrated by the procedure of simply stirring mixtures of imine-linked COFs (seven examples) and KHSO 5 in anhydrous dimethylformamide for several hours to complete the conversions and gram-scale synthesis. The high efficiency of this approach enables facile production of amide COFs from widely available imine-linked COFs, which lays the foundation for exploring practical applications of this unique type of polyamide material.

Exploring new linkage chemistry for covalent organic frameworks (COFs) provides a strong driving force to promote the development of this emerging class of crystalline porous organic materials. Herein we report a strategy to synthesize COFs with azo linkage, one of the most important functional unit in materials science but having not yet been exploited as a linkage of COFs. This strategy is developed on the basis of in situ linker exchange, by which imine-linked COFs are completely transformed into azo-linked COFs (Azo-COFs). Moreover, distinct properties of Azo-COFs from their corresponding imine-linked precursors are observed, indicating unique property of Azo-COFs. This strategy provides a useful approach to develop new linkage chemistry for COFs. It also has established a synthetic method for azo-linked COFs, which not only enriches the family of COFs but also offers a platform to explore properties and applications of this class of crystalline porous conjugated polymers.

Polyamide is an important class of membrane materials for separation technology. The polyamide membranes currently used are amorphous, and thus, their pore structures are disordered, which inevitably decreases their performance in separation. Herein, we report a new type of polyamide membranes which are fabricated from amide-linked covalent organic frameworks (COFs), a class of crystalline porous polymers with well-ordered pore structures. Thanks to the structural advantages of amide-linked COFs, the polyamide COF membranes not only exhibit high permeability (482.3 L m–2 h–1 bar–1 to water) and high rejection rate to organic dyes (>99% for methylene blue) but also display excellent stability under a harsh environment. The vantage of the polyamide COF membranes is also manifested by the comparison of their mechanical property, stability, and separation performance with that of the membranes fabricated from the COFs having the same building blocks but linked with imine and amine linkages. This work demonstrates that amide-linked COFs, which combine the structural features of COFs and polyamide, could be a new type of advanced materials for the fabrication of high-performance separation membranes.