Charge-Transfer-Mediated Mechanism Dominates Oxygen Quenching of Ligand-Protected Noble-Metal Cluster Photoluminescence.

Photoluminescence (PL) quenching of ligand-protected noble-metal clusters (NMCs) by molecular oxygen is often used to define whether the PL of NMC is fluorescent or phosphorescent, and only energy transfer has been always considered as the quenching mechanism. Herein, we performed the Rehm-Weller analysis of the O 2 -induced PL quenching of 13 different NMCs and found that the charge-transfer (CT)-mediated mechanism dominates the quenching process. The quenching rate constant showed a clear dependence on the CT driving force, varied markedly from 10 6 to 10 9 M -1 s -1 . Transient absorption spectroscopy and photon upconversion measurements confirmed the triplet sensitization of aromatic molecules by NMCs regardless of the quenching degree by O 2 , establishing that the PL of NMCs under investigation originates from the excited triplet state (i.e., phosphorescence). The results herein provide an essential indicator for correctly determining whether the PL of an NMC is fluorescent or phosphorescent.