Intrareticular Exciton Effects Regulate Photocatalytic Activity in Donor–Acceptor Olefin‐Linked Covalent Organic Frameworks

Olefin-linked covalent organic frameworks (OL-COFs) show great promise for visible-light-driven photocatalysis. Manipulating atomic-level donor-acceptor interactions in OL-COFs is key to understanding their exciton effects in this system. Here, three OL-COFs are presented with orthorhombic lattice structures, synthesized via Knoevenagel polycondensation reaction of terephthalaldehyde and tetratopic monomers featuring phenyl, benzo[c][1,2,5]oxadiazole, and benzo[c][1,2,5]thiadiazole moieties. These OL-COFs feature tunable donor-acceptor interactions, making them ideal for studying exciton effects in olefin-linked systems. Comprehensive analyses, including temperature-dependent photoluminescence spectra, ultrafast spectroscopy, and theoretical calculations, reveal that stronger donor-acceptor interactions lead to reduced exciton binding energy (E_b), accelerated exciton dissociation, and longer-lived photogenerated charges, thereby enhancing photocatalytic performance. Notably, The TMO-BDA COF, with the lowest E_b, demonstrates superior photocatalytic activity in one-pot sequential organic transformation and excellent catalytic performance in gram-scale reactions, highlighting its potential for practical applications. This work provides valuable insights into regulating the exciton effect at the molecular level in OL-COFs, offering pathways to enhance photocatalytic efficiency.