Enhanced electrochemiluminescent brightness and stability of porphyrins by supramolecular pinning and pinching for sensitive zinc detection.

Ultrasensitive electrochemiluminescence (ECL) detection can benefit substantially from the rational configuration of emitter-enhancer stereochemistry. Here, using zinc(II) meso-5,10,15,20-tetra(4-sulfonatophenyl)porphyrin (ZnTSPP) as a model, we demonstrate that both the ECL intensity and the photostability of this emitter were significantly improved when it was trapped in pyridyl-bridged β-cyclodextrin dimer (Py(CD)); a synthetic enhancer that is ECL inactive. Through NMR characterization, we confirmed that ZnTSPP formed a clam-like inclusion complex involving pinning and pinching forces from the biocompatible container Py(CD). Up to a threefold increase in the ECL brightness of ZnTSPP was witnessed when it was encapsulated in β-CD. Absorption and emission spectroscopic data revealed that both the extended excitation lifetime and the restricted mobility of the guest contributed to the observed improvement in signal transduction within the host molecule. This bioinspired entrapment also led to a marked boost in ECL stability. With the aid of the newly identified coreactant HO, the hollow TSPP@Py(CD) system was employed to create a Zn-selective probe that was capable of sensitive and accurate zinc detection. The observed increase in ECL conversion and enhanced photophysical properties of this compact supramolecular assembly render it a novel template for enhancing ECL in analytical applications. Graphical abstract ᅟ.