• • H2P-BT(OMe)2-COF achieves synergistic electron transfer (ET) and energy transfer (EnT) pathways, enabling selective oxidation of benzylamine to imines with O2 as oxidant, achieving yields above 90% under visible light (λ > 420 nm) at room temperature.
• • The methoxy functionalization in H2P-BT(OMe)2-COF narrows the bandgap by approximately 0.2 eV compared to H2P-BT-COF, enhancing visible-light absorption and increasing the thermodynamic driving force for superoxide radical (O2•−) formation by 0.15 V.
• • The hydrogen-bonding network in H2P-BT(OMe)2-COF facilitates ambipolar charge transfer with charge carrier mobilities up to 0.5 cm2 V−1 s−1, suppressing charge recombination and improving photocatalytic quantum efficiency to 12% at 420 nm.
• • The one-dimensional channels created by polar methoxy groups ensure rapid reactant diffusion, reducing mass transport limitations and enabling turnover numbers (TON) exceeding 1000 for oxidative coupling reactions, outperforming conventional porphyrin photocatalysts by a factor of 5.