Functional conjugated microporous polymers: from 1,3,5-benzene to 1,3,5-triazine

Conjugated microporous polymers (CMPs) based on the electron-withdrawing 1,3,5-triazine node (TCMPs) were synthesized by palladium-catalyzed Sonogashira-Hagihara cross-coupling. The porosity in these polymers was found to be comparable to the analogous 1,3,5-connected benzene CMP systems that we reported previously, demonstrating that nodes can be substituted in these amorphous materials in a rational manner, much as for certain crystalline porous metal–organic frameworks. The CO2 adsorption properties of the TCMPs were measured and compared with the corresponding CMPs, and it was found that the TCMP networks adsorbed more CO2 than CMP analogues with comparable BET surface areas. Network TNCMP-2 showed the highest surface area (995 m2 g−1) and a CO2 uptake of 1.45 mmol g−1 at 1 bar at 298 K. The band gap in these triazine-based CMPs could also be engineered through copolymerization with other functional monomers.