3 years ago

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

Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4′-Bipyridine Gold Nanosphere Oligomers
Vartkess A. Apkarian, Emily A. Sprague-Klein, Michael O. McAnally, Richard P. Van Duyne, George C. Schatz, Tamar Seideman, Dmitry V. Zhdanov, Alyssa B. Zrimsek
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.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b08868

DOI: 10.1021/jacs.7b08868

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