Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4′-Bipyridine Gold Nanosphere Oligomers

We clarify mechanistic questions regarding plasmon-driven chemistry and nanoscale photocatalysis within optically confined near-field plasmonic systems. Using surface-enhanced Raman scattering (SERS), we directly monitor the photoinduced reaction dynamics of 4,4'-bipyridine molecules, localized in plasmonic hot spots within individual gold nanosphere oligomers. Our experiment generates surface electrons from the gold nanoparticle using an intense off-molecular resonance continuous wave pump field, and detects radical anion products via SERS. This is done by adopting a dual-wavelength spectroscopic approach. Empirical evidence of plasmon-driven electron transfer is provided for the first time by direct detection of the 4,4'-bipyridine radical anion species localized in the plasmonic hot spots of individual gold nanosphere oligomers, corroborated by open-shell density functional theory calculations. An isotopologue approach using both protonated and deuterated 4,4'-bipyridine molecules demonstrates the single molecule response of plasmon-driven electron transfer occurring in single nanosphere oligomer systems with a 3% yield, a phenomenon unobserved in ensemble measurements under analogous experimental conditions. This mechanism has broad applicability to using nanoscale chemical reactors for surface redox reactions on the subnanometer scale.