Electron-Transfer Dynamics for a Donor-Bridge-Acceptor Complex in Ionic Liquids

Jessalyn A. DeVine, Marena Labib, Megan E. Harries, Rouba Abdel Malak Rached, Joseph Issa, James F. Wishart, Edward W. Castner

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Abstract

Intramolecular photoinduced electron transfer from an N,N-dimethyl-p-phenylenediamine donor bridged by a diproline spacer to a coumarin 343 acceptor was studied using time-resolved fluorescence measurements in three ionic liquids and in acetonitrile. The three ionic liquids have the bis[(trifluoromethyl)sulfonyl]amide anion paired with the tributylmethylammonium, 1-butyl-1-methylpyrrolidinium, and 1-decyl-1-methylpyrrolidinium cations. The dynamics in the two-proline donor-bridge-acceptor complex are compared to those observed for the same donor and acceptor connected by a single proline bridge, studied previously by Lee et al. (J. Phys. Chem. C 2012, 116, 5197). The increased conformational freedom afforded by the second bridging proline resulted in multiple energetically accessible conformations. The multiple conformations have significant variations in donor-acceptor electronic coupling, leading to dynamics that include both adiabatic and nonadiabatic contributions. In common with the single-proline bridged complex, the intramolecular electron transfer in the two-proline system was found to be in the Marcus inverted regime. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)11336-11345
Number of pages10
JournalJournal of Physical Chemistry B
Volume119
Issue number34
DOIs
Publication statusPublished - Aug 27 2015

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

DeVine, J. A., Labib, M., Harries, M. E., Rached, R. A. M., Issa, J., Wishart, J. F., & Castner, E. W. (2015). Electron-Transfer Dynamics for a Donor-Bridge-Acceptor Complex in Ionic Liquids. Journal of Physical Chemistry B, 119(34), 11336-11345. https://doi.org/10.1021/acs.jpcb.5b03320