Zinc–Salen Anchored Multidentate Two‐Dimensional Metal–Organic Framework for Coupling Photoredox of Oxygen and Benzylamine

Two-dimensional π-conjugated metal-organic frameworks (2D MOFs) are promising solar-driven catalysts, but often suffer from sluggish charge separation due to insufficient strong electron acceptors. To overcome this, two isostructural and heteroporous 2D MOFs, Zn-HTT, and Zn-HTD were built from multidentate Zn─O4 node linkages but differed in active-site design. Zn-HTT integrates anchored chelating Zn─N2O2 Salen moieties and Zn─O4 units, whereas Zn-HTD contains only Zn─O4 nodes. The Zn-Salen units in Zn-HTT narrow the bandgap to 1.99 eV and establish a stronger intramolecular donor-acceptor architecture that drives efficient spatial charge separation. Consequently, Zn-HTT achieves a high hydrogen peroxide (H2O2) photosynthesis rate of 21.9 mmol g-1 h-1 and delivers 94.5% yield of N-benzylbenzaldimine from the benzylamine photooxidation, significantly outperforming Zn-HTD (14.2 mmol g-1 h-1; 85.6% yield). Mechanistic studies confirm that the Zn-Salen sites serve as superior electron-accepting and O2-activating centers, enabling strong *OO intermediate adsorption and highly selective two-electron oxygen reduction to H2O2. Moreover, Zn-HTT exhibits better stability, retaining >91% activity over 10 cycles and showing enhanced thermal resilience, attributable to the robust chelating Zn-Salen linkages. This work demonstrates that integrating metallo-Salen motifs into multidentate 2D MOFs is a viable strategy to boost photocatalytic activity, selectivity, and durability in solar-driven synthesis.