A comparison of electron-transfer dynamics in ionic liquids and neutral solvents

Heather Y. Lee, Joseph B. Issa, Stephan S. Isied, Ed Castner, Yunfeng Pan, Charles L. Hussey, Kwang Soon Lee, James F. Wishart

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

The effect of ionic liquids on photoinduced electron-transfer reactions in a donor-bridge-acceptor system is examined for two ionic liquid solvents, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and tributylmethylammonium bis(trifluoromethylsulfonyl)amide. The results are compared with those for the same system in methanol and acetonitrile solution. Electron-transfer rates were measured using time-resolved fluorescence quenching for the donor-bridge-acceptor system comprising a 1-N,1-N-dimethylbenzene-1,4- diamine donor, a proline bridge, and a coumarin 343 acceptor. The photoinduced electron-transfer processes are in the inverted regime (-ΔG >) in all four solvents, with driving forces of -1.6 to -1.9 eV and estimated reorganization energies of about 1.0 eV. The observed electron-transfer kinetics have broadly distributed rates that are generally slower in the ionic liquids compared to the neutral solvents, which also have narrower rate distributions. To describe the broad distributions of electron-transfer kinetics, we use two different models: a distribution of exponential lifetimes and a discrete sum of exponential lifetimes. Analysis of the donor-acceptor electronic coupling shows that for ionic liquids this intramolecular electron-transfer reaction should be treated using a solvent-controlled electron-transfer model.

Original languageEnglish
Pages (from-to)5197-5208
Number of pages12
JournalJournal of Physical Chemistry C
Volume116
Issue number8
DOIs
Publication statusPublished - Mar 1 2012

Fingerprint

Ionic Liquids
Ionic liquids
electron transfer
Electrons
liquids
Amides
amides
life (durability)
Xylenes
Kinetics
Diamines
kinetics
diamines
Acetonitrile
Proline
acetonitrile
Methanol
Quenching
methyl alcohol
Fluorescence

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Lee, H. Y., Issa, J. B., Isied, S. S., Castner, E., Pan, Y., Hussey, C. L., ... Wishart, J. F. (2012). A comparison of electron-transfer dynamics in ionic liquids and neutral solvents. Journal of Physical Chemistry C, 116(8), 5197-5208. https://doi.org/10.1021/jp208852r

A comparison of electron-transfer dynamics in ionic liquids and neutral solvents. / Lee, Heather Y.; Issa, Joseph B.; Isied, Stephan S.; Castner, Ed; Pan, Yunfeng; Hussey, Charles L.; Lee, Kwang Soon; Wishart, James F.

In: Journal of Physical Chemistry C, Vol. 116, No. 8, 01.03.2012, p. 5197-5208.

Research output: Contribution to journalArticle

Lee, HY, Issa, JB, Isied, SS, Castner, E, Pan, Y, Hussey, CL, Lee, KS & Wishart, JF 2012, 'A comparison of electron-transfer dynamics in ionic liquids and neutral solvents', Journal of Physical Chemistry C, vol. 116, no. 8, pp. 5197-5208. https://doi.org/10.1021/jp208852r
Lee, Heather Y. ; Issa, Joseph B. ; Isied, Stephan S. ; Castner, Ed ; Pan, Yunfeng ; Hussey, Charles L. ; Lee, Kwang Soon ; Wishart, James F. / A comparison of electron-transfer dynamics in ionic liquids and neutral solvents. In: Journal of Physical Chemistry C. 2012 ; Vol. 116, No. 8. pp. 5197-5208.
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