Nitrogen‐Containing Microporous Conjugated Polymers via Carbazole‐Based Oxidative Coupling Polymerization: Preparation,Porosity, and Gas Uptake

Facile preparation of microporous conjugated polycarbazoles via carbazole‐based oxidative coupling polymerization is reported. The process to form the polymer network has cost‐effective advantages such as using a cheap catalyst, mild reaction conditions, and requiring a single monomer. Because no other functional groups such as halo groups, boric acid, and alkyne are required for coupling polymerization, properties derived from monomers are likely to be fully retained and structures of final polymers are easier to characterize. A series of microporous conjugated polycarbazoles ( CPOP‐2–7 ) with permanent porosity are synthesized using versatile carbazolyl‐bearing 2D and 3D conjugated core structures with non‐planar rigid conformation as building units. The Brunauer–Emmett–Teller specific surface area values for these porous materials vary between 510 and 1430 m² g^?1. The dominant pore sizes of the polymers based on the different building blocks are located between 0.59 and 0.66 nm. Gas (H₂ and CO₂) adsorption isotherms show that CPOP‐7 exhibits the best uptake capacity for hydrogen (1.51 wt% at 1.0 bar and 77 K) and carbon dioxide (13.2 wt% at 1.0 bar and 273 K) among the obtained polymers. Furthermore, its high CH₄/N₂ and CO₂/N₂ adsorption selectivity gives polymer CPOP‐7 potential application in gas separation.