Post-synthetic modification of imine linkages of a covalent organic framework for its catalysis application

Post-synthetic modification has been the most powerful strategy for covalent organic frameworks (COFs) for their functionalization in many fields. This strategy is typically achieved through the quantitative reaction between existing reactive sites on the linkers (building units) and incoming functional groups. However, usage of linkages (bonds formed to construct COFs) for the post-synthetic modification still remains limited. Herein, we develop a new post-synthetic modification route that is based on the modification of linkages. With this strategy, the imine linkages of a two-dimensional (2D) COF, TFPPy-PyTTA-COF, have been transformed into amine linkages to give the amine-linked isostructure with retention of crystallinity and porosity. The subsequent aminolysis of the amine linkages with 1,3-propane sultone and further metathetical reaction with cobalt acetate [Co(OAc)₂] enable the introduction of cobalt alkyl sulfonate to the one-dimensional (1D) channel walls of the COF. The resulting ionic COF with coupled Co²⁺ in the frameworks shows excellent catalytic activity and good recyclability towards the cycloaddition reactions of epoxides and CO₂. This strategy is of interest as it opens a way to use linkage modification for exploring the potential of COFs for different applications.