Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids

Boning Wu, Min Liang, Mark Maroncelli, Edward W. Castner

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyanoborate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

Original languageEnglish (US)
Pages (from-to)14790-14799
Number of pages10
JournalJournal of Physical Chemistry B
Volume119
Issue number46
DOIs
StatePublished - Nov 19 2015

Fingerprint

Ionic Liquids
Ionic liquids
Anions
electron transfer
Negative ions
anions
Electrons
liquids
Quenching
Fluorescence
quenching
fluorescence
Acetonitrile
Amides
amides
acetonitrile
Cations
diffusion coefficient
Positive ions
cations

All Science Journal Classification (ASJC) codes

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

Cite this

Wu, Boning ; Liang, Min ; Maroncelli, Mark ; Castner, Edward W. / Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids. In: Journal of Physical Chemistry B. 2015 ; Vol. 119, No. 46. pp. 14790-14799.
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Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids. / Wu, Boning; Liang, Min; Maroncelli, Mark; Castner, Edward W.

In: Journal of Physical Chemistry B, Vol. 119, No. 46, 19.11.2015, p. 14790-14799.

Research output: Contribution to journalArticle

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AB - Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyanoborate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

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