Transition-Metal-Free Synthesis of Conjugated Microporous Polymers via Amine-Catalyzed Suzuki-Miyaura Coupling Reaction

The synthesis of conjugated microporous polymers (CMPs) has been heavily relied on transition-metal-catalysis carbon-carbon coupling reactions, which has shortages in the scarcity and high cost of the noble metal catalysts. Organocatalysis is a representative metal-free route for C-C bond formation, in which the organocatalysts are comprised of earth abundant elements and is thereby promising to be explored in the CMPs synthesis. Herein, we demonstrate the synthesis of CMPs can be achieved via a transition-metal-free amine-catalyzed oraganocatalytic Suzuki-Miyaura coupling reaction for the first time. The method successfully results in CMPs with a wide scope of monomers. The highest surface area of the CMPs could reach 1269 m2 g-1, which is superior to the transition metal catalysis method. The synthesis of acetylene-linked CMP via metal-free condition can also be realized by this method. The resulting CMPs exhibit good gas uptake and photoluminescent properties. This work demonstrates that metal-free organocatalytic reactions are potential and powerful approach for functional CMPs synthesis.