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Luminescent AgAu Alloy Clusters Derived from Ag Nanoparticles – Manifestations of Tunable AuI–CuI Metallophilic Interactions



Luminescent AgAu alloy quantum clusters are synthesized by a simple method that utilizes the galvanic reduction of polydisperse plasmonic silver nanoparticles. The clusters are characterized by ultraviolet–visible (UV/Vis) absorption spectroscopy, photoluminescence (PL) spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and matrix-assisted laser desorption ionization mass spectrometry (MALDI MS). Selective and tunable quenching of cluster luminescence by CuII ions is observed and depends highly on the solvent as well as the protecting ligands. Metal-ion selectivity is exclusively caused by metallophilic interactions with the cluster core, and the tunability depends on the nature of the protecting ligands as well as solvent effects. Detailed XPS and time-resolved luminescence measurements reveal that the tunability of luminescence quenching is achieved by the systematic variation of the metallophilic interactions between the AuI ions of the alloy cluster and CuI ions formed by the reduction of CuII ions by the cluster core. This is the first report of tunable metallophilic interactions between monolayer-protected quantum clusters and a closed-shell metal ion. We hope that these results will draw more attention to the field of quantum cluster–metal ion interactions and provide useful insights into the stability of these clusters, origin of their intense luminescence, mechanisms of metal-ion sensing, and also help in the development of methods for tuning their properties.