Enhanced Electrochemiluminescence of Rod‐Shape 25‐Atom AuAg Nanoclusters through Ligand Engineering

Abstract

AbstractThe pursuit of highly emissive electrochemiluminescence (ECL) luminophores has long been a goal for both understanding mechanism and advancing detection applications. In this study, we employ ligand engineering to boost the ECL performance of bimetallic Au12Ag13 nanoclusters, substituting the PPh3 ligand with P(Ph‐OMe)3. The results demonstrate a 3.6‐fold enhancement in ECL efficiency following ligand exchange when compared to Au12Ag13‐PPh3, particularly in the presence of 1 mM tri‐n‐propylamine (TPrA) as a coreactant – surpassing the performance of the conventional Ru(bpy)32+ luminophore. Voltammetric analysis reveals the presence of both oxidative and reductive ECL signals under sweeping potentials, with corresponding ECL spectra collected. Proposed ECL mechanisms are rooted in the anodic and cathodic activities of Au12Ag13‐P(Ph‐OMe)3 nanoclusters. Notably, this work captures extremely high and transient ECL signals, sequentially activating LUMO and HOMO states, reminiscent of the behavior observed in Au12Ag13‐PPh3. Our findings present a promising strategy to enhance the ECL of metal nanoclusters, holding potential for further applications in sensing and detection.