Morphology control of conjugated microporous polymer networks for visible‐light‐driven oxidative coupling of amines.

Morphology control of conjugated microporous polymer networks (CMPs) has emerged as a promising strategy for enhancing catalytic efficiency and alleviating product contamination in photocatalytic organic transformations. In this contribution, we present the rational design and synthesis of hollow CMPs (hPorSTZ and hPorDTZ) featuring benzothiadiazoles linkages via Sonogashira‐Hagihara cross‐coupling reaction onto the surface of SiO2 microspheres, followed by the elimination of the SiO2 inner templates. By comparing the catalytic performance of hollow and nonhollow materials, we demonstrated the impact of substrate diffusion pathway on visible‐light‐driven oxidative coupling of amines to imines. With a larger specific surface area and variable surface catalytically active sites, the hollow CMPs exhibited efficient reusability, which reduced the consumption of precious resources and achieve faster conversion rates while maintaining reliable recyclability, competing with their nonhollow counterparts. This morphology‐controlled strategy outlines a promising route for diverse organic transformations utilizing stable, efficient, and recyclable metal‐free CMPs. [ABSTRACT FROM AUTHOR]