In situ Self‐Assembly of Zigzag Polyimide Chains to Crystalline Branched Supramolecular Structures with High Surface Area

Crystalline‐branched supramolecular structures (CBSSs) with surface area (Brunauer‐Emmett‐Teller model) up to 350 m2 · g−1 were synthesized by in situ self‐assembly of the zigzag polyimide macromolecules under solvent‐thermal condition. The pore formation mechanism in these polyimides was supposed to be different from any microporous polymers ever reported. Although this family of porous polyimide does not belong to covalent organic frameworks (COFs), their high degree of crystallinity shows the possibilities that the dynamic covalent chemistry for synthesizing COFs could be extended from easily hydrolyzable BO bond to a more stable imido bond. Therefore, we believe that these CBSSs could be useful in many applications, e.g., catalyst carriers and low‐K materials. magnified image