Solvent-controlled intramolecular electron transfer in ionic liquids

Xiang Li, Min Liang, Anjan Chakraborty, Minako Kondo, Mark Maroncelli

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

The rates of excited-state intramolecular electron transfer in 9-(4-biphenyl)-10-methylacridinium (BPAc), crystal violet lactone (CVL), and bianthryl have been measured in a variety of ionic liquids using time-correlated single-photon counting. All three of these reactions had previously been studied in conventional dipolar solvents and their reaction rates shown to be controlled by solvation dynamics. The main focus of this work is to ask whether the same relationships between reaction and solvation times already established in dipolar solvents also apply in ionic liquids. In BPAc+ where reaction conforms to a simple two-state kinetic scheme and reaction rates are easily measured, the result is a clear "yes". In the case of bianthryl, whose spectra reflect the more complex kinetics of a barrierless process, the answer is also yes. In contrast to other recent studies of bianthryl, the present results demonstrate that the same equality between (integral) reaction times and solvation times observed in conventional solvents also applies in ionic liquids. Finally, the case of CVL is less clear due to the greater uncertainty associated with the data afforded by this weak fluorophore, combined with a lack of data in conventional solvents having large solvation times. But the CVL reaction can also be reasonably interpreted as exhibiting a common behavior in dipolar and ionic solvents.

Original languageEnglish (US)
Pages (from-to)6592-6607
Number of pages16
JournalJournal of Physical Chemistry B
Volume115
Issue number20
DOIs
StatePublished - May 26 2011

Fingerprint

Ionic Liquids
Ionic liquids
Solvation
electron transfer
solvation
Electrons
liquids
reaction time
Crystals
Reaction rates
reaction kinetics
crystals
Kinetics
Fluorophores
kinetics
Excited states
counting
Photons
photons
excitation

All Science Journal Classification (ASJC) codes

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

Cite this

Li, Xiang ; Liang, Min ; Chakraborty, Anjan ; Kondo, Minako ; Maroncelli, Mark. / Solvent-controlled intramolecular electron transfer in ionic liquids. In: Journal of Physical Chemistry B. 2011 ; Vol. 115, No. 20. pp. 6592-6607.
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Solvent-controlled intramolecular electron transfer in ionic liquids. / Li, Xiang; Liang, Min; Chakraborty, Anjan; Kondo, Minako; Maroncelli, Mark.

In: Journal of Physical Chemistry B, Vol. 115, No. 20, 26.05.2011, p. 6592-6607.

Research output: Contribution to journalArticle

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