• • MCOF-E achieves an aniline production rate of 4.90 mM h−1 in nitrobenzene hydrogenation, with ~100% conversion and >99% selectivity, outperforming MCOF-Z and other contrast materials, demonstrating superior photocatalytic efficiency.
• • The E/Z linkage modes in MCOF-E and MCOF-Z result in distinct stacking structures, leading to differences in light absorption and charge transfer, which are critical for optimizing photocatalytic performance.
• • Density functional theory calculations reveal that MCOF-E has a narrower band gap than MCOF-Z, facilitating more efficient generation of photo-induced carriers and accelerating reaction kinetics.
• • The isomerization approach in MCOFs provides a novel strategy to tune photocatalytic properties, offering a pathway for rational design of high-performance materials for solar-driven chemical transformations.