Guest Molecular Assembly Strategy in Covalent Organic Frameworks for Electrochemiluminescence Sensing of Uranyl

Abstract

The application of covalent organic frameworks (COFs) in electrochemiluminescence (ECL) is promising in environmental monitoring. Developing an emerging design strategy to expand the class of COF-based ECL luminophores is highly desirable. Here, a COF-based host-guest system was constructed through guest molecular assembly to deal with nuclear contamination analysis. The efficient charge transport network was formed by inserting an electron-withdrawing guest tetracyanoquinodimethane (TCNQ) into the open space of the COF host (TP-TBDA; TP = 2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde and TBDA = 2,5-di(thiophen-2-yl)benzene-1,4-diamine) with an electron-donating property; the construction of the COF-based host-guest system (TP-TBDA@TCNQ) triggered the ECL emission of non-emitting TP-TBDA. Furthermore, the dense active sites in TP-TBDA were utilized to capture the target substance UO₂²⁺. The presence of UO₂²⁺ broke the charge-transfer effect in TP-TBDA@TCNQ, resulting in the weakening of the ECL signal, thus the established ECL system integrating the low detection limit with high selectivity monitors UO₂²⁺. This COF-based host-guest system provides a novel material platform for constructing late-model ECL luminophores and creates an opportunity for the vigorous ECL technology.