TY - JOUR
T1 - Plasmon-Mediated Intramolecular Methyl Migration with Nanoscale Spatial Control
AU - Brooks, James L.
AU - Warkentin, Christopher L.
AU - Chulhai, Dhabih V.
AU - Goodpaster, Jason D.
AU - Frontiera, Renee R.
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/12/22
Y1 - 2020/12/22
N2 - Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C-N bond and forming a new C-C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. This work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.
AB - Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C-N bond and forming a new C-C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. This work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.
KW - methyl migration
KW - nanoscale patterning
KW - plasmon-driven chemistry
KW - plasmonic photocatalysis
KW - spatial control
KW - surface-enhanced Raman spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85097747250&partnerID=8YFLogxK
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U2 - 10.1021/acsnano.0c07123
DO - 10.1021/acsnano.0c07123
M3 - Article
C2 - 33296172
AN - SCOPUS:85097747250
SN - 1936-0851
VL - 14
SP - 17194
EP - 17202
JO - ACS nano
JF - ACS nano
IS - 12
ER -