Molecular Triplet Generation Enabled by Adjacent Metal Nanoparticles.

High-efficiency generation of spin-triplet states in organic molecules is of great interest in diverse areas such as photocatalysis, photodynamic therapy, and upconversion photonics. Recent studies have introduced colloidal semiconductor nanocrystals as a new class of photosensitizers that can efficiently transfer their photoexcitation energy to molecular triplets. Here, we demonstrate that metallic Ag nanoparticles can also assist in the generation of molecular triplets in polycyclic aromatic hydrocarbons (PAHs), but not through a conventional sensitization mechanism. Instead, the triplet formation is mediated by charge-separated states resulting from hole transfer from photoexcited PAHs (anthracene and pyrene) to Ag nanoparticles, which is established through the rapid formation and subsequent decay of molecular anions revealed in our transient absorption measurements. The dominance of hole transfer over electron transfer, while both are energetically allowed, could be attributed to a Marcus inverted region of charge transfer. Owing to the rapid charge separation and the rapid spin-flip in metals, the triplet formation yields are remarkably high, as confirmed by their engagement in production of singlet oxygen with a quantum efficiency reaching 58.5%. This study not only uncovers the fundamental interaction mechanisms between metallic nanoparticles and organic molecules in both charge and spin degrees of freedom but also greatly expands the scope of triplet "sensitization" using inorganic nanomaterials for a variety of emerging applications.