Pore Space Partition Synthetic Strategy in Imine-linked Multivariate Covalent Organic Frameworks

Partitioning the pores of covalent organic frameworks (COFs) is an attractive strategy for introducing microporosity and achieving new functionality, but it is technically challenging to achieve. Herein, we report a simple strategy for partitioning the micropores/mesopores of multivariate COFs. Our approach relies on the predesign and synthesis of multicomponent COFs through imine condensation reactions with aldehyde groups anchored in the COF pores, followed by inserting additional symmetric building blocks (with C₂ or C₃ symmetries) as pore partition agents. This approach allowed tetragonal or hexagonal pores to be partitioned into two or three smaller micropores, respectively. The synthesized library of pore-partitioned COFs was then applied for the capture of iodine pollutants (i.e., I₂ and CH₃I). This rich inventory allowed deep exploration of the relationships between the COF adsorbent composition, pore architecture, and adsorption capacity for I₂ and CH₃I capture under wide-ranging conditions. Notably, one of our developed pore-partitioned COFs (COF 3-2P) exhibited greatly enhanced dynamic I₂ and CH₃I adsorption performances compared to its parent COF (COF 3) in breakthrough tests, setting a new benchmark for COF-based adsorbents. Results present an effective design strategy toward functional COFs with tunable pore environments, functions, and properties.