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

Ya-Jie Li,Qiong Wu,Jian-Ding Qiu,Qiu-Xia Luo,Wei-Rong Cui,Qiao-Qiao Jiang,Ru-Ping Liang

doi:10.1038/s41467-021-25013-8

Ya-Jie Li, Qiong Wu + Show 5 more

Open Access

https://doi.org/10.1038/s41467-021-25013-8

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Journal: Nature Communications	Publication Date: Aug 5, 2021
Citations: 98	License type: open-access

Affiliation: Nanchang University, Pingxiang University

Abstract

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 C2v or C3v 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.

Highlights

Electrochemiluminescence (ECL) plays a key role in analysis and sensing because of its high sensitivity and low background
The models proposed for the tris(4-formylphenyl) amine (TPA)-DCTP, TFPT-DCTP, TFPB-DCTP, DAFB-DCTP, BTTADCTP, and DAFB-TMT series covalent organic frameworks (COFs) are in PM space group, the BDA-DCTP, TDA-DCTP, and EDA-DCTP series COFs are in P2/M space group, the TPA-TMT, TFPT-TMT, TFPB-TMT, and BTTA-TMT series COFs are in P6 space group, and the BDATMT, TDA-TMT, and EDA-TMT are in P6/M space group (Supplementary Tables 1–18)
The morphological properties were studied by the scanning electron microscope (SEM), which showed that all the COFs possess an analogous fibrillar crystal morphology, uniform diameter (~40 nm), and length of several micrometers (Supplementary Figs. 31–35)

Summary

Introduction

Electrochemiluminescence (ECL) plays a key role in analysis and sensing because of its high sensitivity and low background. 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. Yuan’s group observed ECL of COF nanosheet with co-reactant S2O82− and coreaction accelerator Bu4NPF6, which topologically linked the aggregation-caused quenching ECL luminophores (pyrene) and AIE groups[8] Their COFs only had very low ECL signals. Systematic induction and methodology research on COF-based

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Conclusion