Photochemical synthesis of fluorescent Au₁₆(RGDC)₁₄ and excited state reactivity with molecular oxygen

Aqueous metal nanoclusters have emerged as effective materials for biomedical imaging and therapy. Among them, gold nanoclusters (AuNCs) have been widely studied due to their unique electronic structures. These nanoclusters are often optically impure, comprising a mixture of fluorescent clusters with different metal/ligand compositions. The polydispersity of nanoclusters makes it challenging to isolate the most stable structure, and poses further risks for eventual clinical applications. Herein, Au₁₆L₁₄ clusters are reported which are optically pure as assessed by fluorescence excitation-emission matrix (EEM) spectroscopy and parallel factor (PARAFAC) analysis. The reactivity of their excited state with molecular oxygen was also probed, demonstrating that the Au₁₆L₁₄ clusters generate type I reactive oxygen species (ROS), which can make them effective sensitizers for photodynamic therapy.