Vinylene-bridged donor-acceptor type porous organic polymers for enhanced photocatalysis of amine oxidative coupling reactions under visible light.

Porous organic polymers (POPs), owing to their abundant porosity, high stability and well-tunable properties, are promising candidates as heterogeneous photocatalysts for organic transformations. Here we report two vinylene-bridged donor-acceptor (D-A) structural POPs (TpTc-POP and TbTc-POP) that are facilely constructed by the electron-rich triarylamine and electron-deficient tricyanomesitylene as key building blocks by the organic base catalyzed Knoevenagel condensation. Both TpTc-POP and TbTc-POP possess hierarchical meso- and micro-pores with a high surface area. Furthermore, the unsubstituted vinylene linkages of D-A moieties in their polymer backbones extend their π-conjugation and render their broad absorption range in the visible-light region. Thus, these DA-POPs exhibited highly effective photocatalytic activities for aerobic oxidative coupling of amines to imines under visible light irradiation. This study shows the great potential of conjugated POPs with a D-A structural feature in designing highly efficient and active heterogeneous photocatalytic systems.