Deciphering a volcano-shaped relationship between radical stability and reticular electrochemiluminescence

Abstract Electrochemiluminescence (ECL) is a light-emitting process in which the stability of electrochemically generated radicals has a crucial impact on the efficiency and durability of excited state generation. Therefore, deciphering a relationship between radical stability and ECL performance is...

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Main Authors: Haocheng Xu, Rengan Luo, Haifeng Lv, Tianrui Liu, Qiaobo Liao, Yandong Wang, Ziyan Zhong, Xiaojun Wu, Jianping Lei, Kai Xi
Format: Article
Language:English
Published: Nature Portfolio 2025-02-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-56009-3
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Summary:Abstract Electrochemiluminescence (ECL) is a light-emitting process in which the stability of electrochemically generated radicals has a crucial impact on the efficiency and durability of excited state generation. Therefore, deciphering a relationship between radical stability and ECL performance is highly appealing. In this work, three sp2 carbon-conjugated covalent organic framework (COF) reticular nanoemitters compositing of same pyrene luminophores but different acrylonitrile linkers are designed with progressive electron affinities, named as CN-COF-1, 2, and 3. By precisely modulating the electron affinity of CN-COFs, a volcano relationship between ECL and radical stability is discovered with 78 folds enhancement in ECL intensity. Density functional theoretical calculations indicate that CN-COF-2 exhibits moderate radical stabilization capacity as well as efficient electron transport between the pyrene cores, facilitating ECL generation. Significantly, the appropriate radical stability of CN-COF-2 not only achieves the self-enhanced cathodic ECL but also promotes durability of the ECL intensity. The rational regulation of radical stability paves the way for developing efficient reticular nanoemitters and decoding the ECL fundamentals.
ISSN:2041-1723