Abstract Constitutional isomerism in covalent organic frameworks (COFs) has shown promise for enhancing material properties, especially for photocatalytic applications. Herein, we design two isomeric multicomponent COFs (MC-COFs) via Schiff-base condensation followed by a Povarov reaction to convert the imine linkages into quinoline structures. These isomeric MC-COFs possess opposing C=N bond orientations and differently aligned phenyl groups within COF pores, leading to distinct torsion angles in COF layers. Structural analysis reveals that the enhanced planarity of COFs promotes π-π stacking and electron delocalization, resulting in a favorable band structure and reduced exciton binding energy. Consequently, the COFs achieve a superior hydrogen peroxide (H 2 O 2 ) production rate of 3128 µmol g −1 h −1 under visible light. This study underscores the critical influence of structural isomerism on the photocatalytic efficiency of MC-COFs and provides insights for optimizing COF-based photocatalytic systems.
Cai et al. (Fri,) studied this question.