Reticular Ratchets for Directing Electrochemiluminescence

作者：Rengan Luo, Xiao Luo, Haocheng Xu, Sushu Wan, Haifeng Lv, Beier Zou, Yufei Wang, Tianrui Liu, Chuang Wu, Qizhou Chen, Siqi Yu, Pengfei Dong, Yuxi Tian, Kai Xi, Shuai Yuan, Xiaojun Wu, Huangxian Ju, Jianping Lei · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.4c03981 · 被引用次数：51 · 研究领域：Advanced biosensing and bioanalysis techniques、Electrochemical Analysis and Applications、Covalent Organic Framework Applications

Electrochemiluminescence (ECL) involves charge transfer between electrochemical redox intermediates to produce an excited state for light emission. Ensuring precise control of charge transfer is essential for decoding ECL fundamentals, yet guidelines on how to achieve this for conventional emitters remain unexplored. Molecular ratchets offer a potential solution, as they enable the directional transfer of energy or chemicals while impeding the reverse movement. Herein, we designed 10 pairs of imine-based covalent organic frameworks as reticular ratchets to delicately manipulate the intrareticular charge transfer for directing ECL transduction from electric and chemical energies. Aligning the donor and acceptor (D-A) directions with the imine dipole effectively facilitates charge migration, whereas reversing the D-A direction impedes it. Notably, the ratchet effect of charge transfer directionality intensified with increasing D-A contrast, resulting in a remarkable 680-fold improvement in the ECL efficiency. Furthermore, dipole-controlled exciton binding energy, electron/hole decay kinetics, and femtosecond transient absorption spectra identified the electron transfer tendency from the N-end toward the C-end of reticular ratchets during ECL transduction. An exponential correlation between the ECL efficiency and the dipole difference was discovered. Our work provides a general approach to manipulate charge transfer and design next-generation electrochemical devices.