Ligand Engineering of Bifunctional Metal–Organic Layers for Light-Driven Chemoenzymatic Catalysis

Light-driven chemoenzymatic catalysis combines the selectivity of enzymes with the reactivity of photocatalysts but is often limited by photodegradation, enzyme-photosensitizer incompatibility, and limited recyclability. A ligand-engineered zirconium-based bifunctional metal–organic layer (MOL) was developed that integrates visible-light photocatalysis with enzyme immobilization. By incorporating nitrogen-rich, π-conjugated ligands with donor–acceptor motifs, the resulting MOL exhibits enhanced light harvesting, efficient charge separation, and accelerated triplet exciton generation via the heavy-atom effect for catalyzing alkene isomerization. Simultaneously, the positively charged MOL surface enables a high enzyme loading (up to 0.99 g/g) while retaining enzymatic activity. The optimized Zr-TPMT/OYE2 system demonstrates tandem catalysis: light-driven Z-to-E isomerization followed by enantioselective reduction, yielding almost complete conversion and >99% ee for β-cyanoacrylate derivatives. Mechanistic studies reveal accelerated intersystem crossing and Dexter energy transfer from MOL to substrates, while balanced interfacial interactions preserved enzyme conformation. The system maintains high performance over eight reaction cycles, demonstrating reliable recyclability. This work offers a generalizable strategy for integrating photocatalysis and biocatalysis to achieve asymmetric synthesis under mild conditions.