Transition-metal-free radical homocoupling polymerization to synthesize conjugated poly(phenylene butadiynylene) polymers

Conjugated microporous polymers (CMPs) are porous polymers that have attracted enormous scientific and technical interest in gas adsorption and heterogeneous catalysis. However, most of these conjugated porous polymers involve transition-metal catalysis, and the transition-metal-free radical polymerization method has rarely been investigated. Here, we report the synthesis of conjugated poly(phenylene butadiynylene) polymers by an efficient transition-metal-free radical homocoupling polymerization method. The materials synthesized by this method can achieve high surface areas of up to 1477 m2 g-1, which are superior to those of the reported transition-metal catalysis methods. These highly porous materials showed an excellent capacity for carbon dioxide and hydrogen uptake. This work provides a new methodology to construct high-surface-area organic porous materials.