Electrochemically Lighting Up Luminophores at Similar Low Triggering Potentials with Mechanistic Insights.

Electrochemiluminescence (ECL) with high electrode compatibility and less electrochemical interference has conventionally been envisioned by lowering the oxidative potential of luminophores and/or screening luminophores with a low oxidative potential. Herein, an alternative was developed by employing the environmental-friendly carbohydrazide as a coreactant, which enabled serial luminophores with oxidative-reduction ECL at one similar low triggering potential around 0.55 V versus Ag/AgCl, including Ru(bpy) as well as CdTe, CdSe, CuInS/ZnS, and Au nanocrystals. Because the eight-electron releasing process of carbohydrazide was electrochemically triggered at ∼0.25 V versus Ag/AgCl, the radicals generated via electrochemical oxidation of carbohydrazide could reduce the luminophores at a much lower potential than those of traditional coreactants. All the luminophore/carbohydrazide systems exhibited one ECL process around 0.55 V, which was about 0.65 V lower than that of a traditional Ru(bpy)/tri--propylamine system (typically around +1.2 V), and even lower than the oxidative potential of some luminophores. The ECL of the luminophore/carbohydrazide system was spectrally close to that of the corresponding luminophore/tri--propylamine system; the maximum emission wavelength of the low triggering potential ECL could shift from 540 to 783 nm via the selection of luminophores in this case. The coreactant screening strategy would be a favorable addition to the expected luminophore screening strategy for achieving enhanced ECL performance. This work created an avenue toward a deeper understanding of the ECL mechanism.