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 O2-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 106 to 109 M-1s-1. Transient absorption spectroscopy and photon upconversion measurements confirmed the triplet sensitization of aromatic molecules by NMCs regardless of the quenching degree by O2, 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.

Automated summary

The charge-transfer mediated mechanism dominates the photoluminescence (PL) quenching process of ligand-protected noble-metal clusters (NMCs) induced by molecular oxygen. Transient absorption spectroscopy and photon upconversion measurements confirm the phosphorescent nature of the PL of these NMCs, providing an essential indicator for determining their photoluminescence properties.