Annihilation Electrochemiluminescence Triggered by Bipolar Electrochemistry

Bipolar electrochemistry (BE) combined with electrochemiluminescence (ECL) has gained considerable attention as a versatile and powerful analytical technique operating in a wireless manner. However, only co‐reactant ECL has been reported so far when using a BE setup. In this work, the generation of annihilation ECL at the anodic extremity of a bipolar electrode (BPE) is demonstrated in two different spatial arrangements of the electrodes. The reported approach is based on a synergetic effect between the asymmetric electroactivity induced across the BPE, which produces different redox states of [Ru(bpy)3]2+, and the electro‐migration mechanism of the formed ionic species, allowing the localization and concentration of the ECL emission. The presented approach demonstrating annihilation ECL via BE, paves the way for the design of easy and straightforward light‐emitting platforms for multiple applications. The generation of annihilation electrochemiluminescence (ECL) was achieved via bipolar electrochemistry by taking advantage of the asymmetric electroactivity induced across the bipolar electrode, generating different redox states of [Ru(bpy)3]2+, and the electro‐migration of the formed ionic species.