Bimodal Oxidation Electrochemiluminescence Mechanism of Coreactant‐Embedded Covalent Organic Frameworks via Postsynthetic Modification

Abstract Electrochemiluminescence (ECL) efficiency is determined by charge transfer between coreactants and emitters in coreactant systems, which are usually limited by their slow intermolecular charge transfer. In this study, a covalent organic framework (COF) with aldehyde residue was synthesized, and then coreactants were covalently integrated into the skeleton through the postsynthetic modification strategy, resulting in a crystalline coreactant‐embedded COF nanoemitter (C–COF). Compared to the pristine COF with an equivalent external coreactant, C–COF exhibited an extraordinary 1008‐fold enhancement of ECL intensity due to the rapid intrareticular charge transfer. Significantly, with the pH increase, C–COF shows protonation‐induced ECL enhancement for the first ECL peaked at +1.1 V and an opposite trend for the second ECL at +1.4 V, which were attributed to the antedating oxidation of coreactant in framework and COF self‐oxidation, respectively. The resulting bimodal oxidation ECL mechanism was rationalized by spectral characterization and density functional theory calculations. The postsynthetic coreactant‐embedded nanoemitters present innovative and universal avenues for advancing ECL systems.