Modulating the Electron Affinity of Small Bipyridyl Molecules on Single Gold Nanoparticles for Plasmon-Driven Electron Transfer

Sprague-Klein, Emily A.; Ho-Wu, Rosina; Nguyen, Duc; Coste, Scott C.; Wu, Yue; McMahon, John J.; Seideman, Tamar; Schatz, George C.; Van Duyne, Richard P.

doi:10.1021/acs.jpcc.1c07803

Title: Modulating the Electron Affinity of Small Bipyridyl Molecules on Single Gold Nanoparticles for Plasmon-Driven Electron Transfer

Journal Article · Thu Sep 30 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c07803· OSTI ID:1865055

^[1]; Ho-Wu, Rosina ^[2];

^[3]; Coste, Scott C. ^[4];

^[2]; McMahon, John J. ^[5]; Seideman, Tamar ^[2];

^[2];

^[2]

Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); Intel Corporation, Hillsboro, OR (United States)
Northwestern Univ., Evanston, IL (United States); Yale Univ., New Haven, CT (United States)
Fordham Univ., Rose Hill Bronx, NY (United States)

Developing controlled platforms for plasmon-driven chemistry is of great importance in catalytic reactions at the nanoscale. We report anion radical formation for five bipyridyl complexes of varying degrees of electron affinity utilizing optically fo-cused intraband (594 nm) and interband (532 nm) pump excitation of single gold nanoparticles. The surface-enhanced Raman scattering (SERS) of anion radicals for the five non-resonant adsorbed molecules 2,2’-bipyridine (22BPY), 4,4’-bipyridine (44BPY), trans-1,2-bis(4-pyridyl)ethylene (BPE), 1,2-bis(4-pyridyl)acetylene (BPA), and 1,2-bis(4-pyridyl)ethane (BPEt) were detected using localized surface-plasmon resonance (LSPR) excitation with 785 nm. The electron affinity of the five bipyridyl complexes were determined using electrochemistry. Molecules with low electron affinity experienced high-er instances of radical anion formation under a plasmon-coupled intraband electron transfer excitation (594 nm) whereas molecules with high electron affinity showed a preference for anion radical formation under direct interband electron trans-fer excitation (532 nm). The lowest unoccupied molecular orbital (LUMO) energy levels for low electron affinity surface-bound molecules (22BPY, BPEt) are on average ~0.43 eV higher for high electron affinity surface-bound molecules (BPA, BPE, 44BPY) as calculated using time-dependent density functional theory, elucidating the importance of plasmon coupling to energy levels that facilitate charge transfer pathways. We also show the ability to ‘activate’ high vs low electron affinity single nanoparticles with the choice of pump excitation wavelength. The findings show the complex interplay between molecular electron affinity, orbital overlap with the density of states of the plasmonic metal, and excitation energetics of the pump laser wavelength. Potential applications of this work include enhanced control over molecular scale catalysis, biosensor design, and solar energy capture.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: SC0004752; CHE-1414466; CHE-1465201

OSTI ID:: 1865055

Alternate ID(s):: OSTI ID: 1866206

Journal Information:: Journal of Physical Chemistry. C, Vol. 125, Issue 40; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
bipyridyl
gold nanoparticles
plasmon-driven chemistry
surface-enhanced Raman spectroscopy
cyclic voltammetry
single nanoparticle two-color SERS
charge transfer
molecules
nanoparticles
anions
Raman spectroscopy

Title: Modulating the Electron Affinity of Small Bipyridyl Molecules on Single Gold Nanoparticles for Plasmon-Driven Electron Transfer

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