Coordination-Induced Emissive Poly-NHC-Derived Metallacage for Pesticide Detection

Developing sensitive, rapid, and convenient methods for the detection of residual toxic pesticides is immensely important to prevent irreversible damage to the human body. Luminescent metal-organic cages and macrocycles have shown great applications, and designing highly emissive supramolecular systems in dilute solution using metal-ligand coordination-driven self-assembly is demanded. In this study, we have demonstrated the development of a silver-carbene bond directed tetranuclear silver(I)-octacarbene metallacage [Ag₄(L)₂](PF₆)₄ (1) based on an aggregation-induced emissive (AIE) cored 1,1',1″,1‴-((1,4-phenylenebis(ethene-2,1,1-triyl))tetrakis(benzene-4,1-diyl))tetrakis(3-methyl-1H-imidazol-3-ium) salt (L). A 36-fold enhanced emission was observed after metallacage (1) formation when compared with the ligand (L) in dilute solution due to the restriction of intramolecular motions imparted by metal-ligand coordination. Such an increase in fluorescence made 1 a potential candidate for the detection of a broad-spectrum pesticide, 2,6-dichloro-nitroaniline (DCN). 1 was able to detect DCN efficiently by the fluorescence quenching method with a significant detection limit (1.64 ppm). A combination of static and dynamic quenching was applicable depending on the analyte concentration. The use of silver-carbene bond directed self-assembly to exploit coordination-induced emission as an alternative to AIE in dilute solution and then apply this approach to solve health and safety concerns is noteworthy and carries a lot of potential for future developments.