Diaryl Dihydrophenazine‐Based Porous Organic Polymers Enhance Synergistic Catalysis in Visible‐Light‐Driven Organic Transformations

Abstract Porous organic polymers (POPs) have emerged as a novel class of porous materials that are synthesized by the polymerization of various organic monomers with different geometries and topologies. The molecular tunability of organic building blocks allows the incorporation of functional units for photocatalytic organic transformations. Here, we report the synthesis of two POP‐based photocatalysts via homopolymerization of vinyl‐functionalized diaryl dihydrophenazine (DADHP) monomer ( POP1 ) and copolymerization of vinyl‐functionalized DADHP and 2,2′‐bipyridine monomers ( POP2 ). The fluorescence lifetimes of DADHP units in the POPs significantly increased, resulting in enhanced photocatalytic performances over homogeneous controls. POP1 is highly effective in catalysing visible‐light‐driven C−N bond forming cross‐coupling reactions. Upon coordination with Ni 2+ ions, POP2‐Ni shows strong synergy between photocatalytic and Ni catalytic cycles due to the confinement effect within the POP framework, leading to high efficiency in energy, electron, and organic radical transfer. POP2‐Ni displays excellent activity in catalysing C−P bond forming reactions between diarylphosphine oxides and aryl iodides. They increased the photocatalytic activities by more than 30‐fold in C−N and C−P cross‐coupling reactions. These POP catalysts were readily recovered via centrifugal separation and reused in six catalytic cycles without loss of activities. Thus, photosensitizer‐based POPs provide a promising platform for heterogeneous photocatalytic organic transformations.