A general design approach toward covalent organic frameworks for highly efficient electrochemiluminescence

Electrochemiluminescence (ECL) plays a key role in analysis and sensing because of its high sensitivity and low background. Its wide applications are however limited by a lack of highly tunable ECL luminophores. Here we develop a scalable method to design ECL emitters of covalent organic frameworks (COFs) in aqueous medium by simultaneously restricting the donor and acceptor to the COFs' tight electron configurations and constructing high-speed charge transport networks through olefin linkages. This design allows efficient intramolecular charge transfer for strong ECL, and no exogenous poisonous co-reactants are needed. Olefin-linked donor-acceptor conjugated COFs, systematically synthesized by combining non-ECL active monomers with C-2v or C-3v symmetry, exhibit strong ECL signals, which can be boosted by increasing the chain length and conjugation of monomers. The present concept demonstrates that the highly efficient COF-based ECL luminophores can be precisely designed, providing a promising direction toward COF-based ECL phosphors. Electrochemiluminescence (ECL) plays a key role in analysis and sensing but its application is limited by a lack of highly tunable luminophores. Here, the authors demonstrate the design of high efficient ECL luminophores of covalent organic frameworks (COFs) in aqueous media by simultaneously restricting the donor and acceptor to the COFs' electron configurations and constructing charge transport networks through olefin linkages.