Integration of Perylene Diimide into a Covalent Organic Framework for Photocatalytic Oxidation

Abstract Perylene diimides (PDIs) have garnered considerable attention due to their immense potential in photocatalysis. However, manipulating the molecular packing within their aggregates and enhancing the efficiency of photogenerated carrier recombination remain significant challenges. In this study, we demonstrate the incorporation of a PDI unit into a covalent organic framework (COF), named PDI‐PDA, by linking an ortho‐substituted PDI with p ‐phenylenediamine (PDA) to control its intermolecular aggregation. The incorporation enables precise modulation of electron‐transfer dynamics, leading to a ten‐fold increase in the efficiency of photocatalytic oxidation of thioether to sulfoxide with PDI‐PDA compared to the PDI molecular counterpart, with yields exceeding 90 %. Electron property studies and density functional theory calculations show that the PDI‐PDA with its well‐defined crystal structure, enhances π–π stacking and lowers the electron transition barrier. Moreover, the strong electron‐withdrawing ability of the PDI unit promotes the spatial separation of the valency band maximum and conduction band minimum of PDI‐PDA, suppressing the rapid recombination of photogenerated electron‐hole pairs and improving the charge‐separation efficiency to give high photocatalytic efficiency. This study provides a brief but effective way for improving the photocatalytic efficiency of commonly used PDI‐based dyes by integrating them into a framework skeleton.