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

Emily A. Sprague-Klein; Michael O. McAnally; Dmitry V. Zhdanov; Alyssa B. Zrimsek; Vartkess A. Apkarian; Tamar Seideman; George C. Schatz; Richard P. Van Duyne

doi:10.1021/jacs.7b08868

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

Emily A. Sprague-Klein, Michael O. McAnally, Dmitry V. Zhdanov, Alyssa B. Zrimsek, Vartkess A. Apkarian, Tamar Seideman, George C. Schatz, Richard P. Van Duyne^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

60 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	15212-15221
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	139
Issue number	42
DOIs	https://doi.org/10.1021/jacs.7b08868
State	Published - Oct 25 2017

Funding

E.A.S.-K., M.O.M., V.A.A., G.C.S., and R.P.V.D. were supported by the National Science Foundation Center for Chemical Innovation dedicated to Chemistry at the Space-Time Limit (CaSTL) Grant CHE-1414466. E.A.S.-K. and M.O.M. acknowledge support from the National Science Foundation Graduate Research Fellowship Program (DGE-0824162). D.V.Z. and T.S. acknowledge support from the National Science Foundation Grant CHE-1465201. A.B.Z. and R.P.V.D. acknowledge support from the National Science Foundation (CHE-1506683). The authors would also like to thank Northwestern University’s Atomic and Nanoscale Characterization Experimental Center (NUANCE) for the use of their imaging facilities.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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Sprague-Klein, E. A., McAnally, M. O., Zhdanov, D. V., Zrimsek, A. B., Apkarian, V. A., Seideman, T., Schatz, G. C., & Van Duyne, R. P. (2017). Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4′-Bipyridine Gold Nanosphere Oligomers. Journal of the American Chemical Society, 139(42), 15212-15221. https://doi.org/10.1021/jacs.7b08868

@article{e91fb030abad460b8fd593f3398f5101,

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

abstract = "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.",

author = "Sprague-Klein, \{Emily A.\} and McAnally, \{Michael O.\} and Zhdanov, \{Dmitry V.\} and Zrimsek, \{Alyssa B.\} and Apkarian, \{Vartkess A.\} and Tamar Seideman and Schatz, \{George C.\} and \{Van Duyne\}, \{Richard P.\}",

note = "Funding Information: E.A.S.-K., M.O.M., V.A.A., G.C.S., and R.P.V.D. were supported by the National Science Foundation Center for Chemical Innovation dedicated to Chemistry at the Space-Time Limit (CaSTL) Grant CHE-1414466. E.A.S.-K. and M.O.M. acknowledge support from the National Science Foundation Graduate Research Fellowship Program (DGE-0824162). D.V.Z. and T.S. acknowledge support from the National Science Foundation Grant CHE-1465201. A.B.Z. and R.P.V.D. acknowledge support from the National Science Foundation (CHE-1506683). The authors would also like to thank Northwestern University{\textquoteright}s Atomic and Nanoscale Characterization Experimental Center (NUANCE) for the use of their imaging facilities. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/jacs.7b08868",

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T1 - Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4′-Bipyridine Gold Nanosphere Oligomers

AU - Sprague-Klein, Emily A.

AU - McAnally, Michael O.

AU - Zhdanov, Dmitry V.

AU - Zrimsek, Alyssa B.

AU - Apkarian, Vartkess A.

AU - Seideman, Tamar

AU - Schatz, George C.

AU - Van Duyne, Richard P.

N1 - Funding Information: E.A.S.-K., M.O.M., V.A.A., G.C.S., and R.P.V.D. were supported by the National Science Foundation Center for Chemical Innovation dedicated to Chemistry at the Space-Time Limit (CaSTL) Grant CHE-1414466. E.A.S.-K. and M.O.M. acknowledge support from the National Science Foundation Graduate Research Fellowship Program (DGE-0824162). D.V.Z. and T.S. acknowledge support from the National Science Foundation Grant CHE-1465201. A.B.Z. and R.P.V.D. acknowledge support from the National Science Foundation (CHE-1506683). The authors would also like to thank Northwestern University’s Atomic and Nanoscale Characterization Experimental Center (NUANCE) for the use of their imaging facilities. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/10/25

Y1 - 2017/10/25

N2 - 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.

AB - 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.

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ER -

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

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