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Title: Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids

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 tetracyano-borate. 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. Finally, application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V 0, where D is the relative diffusion coefficient between donor and acceptor and V 0 is the value of the electronic coupling at donor-acceptor contact.
Authors:
 [1] ;  [1] ;  [2] ;  [1]
  1. Rutgers Univ., Piscataway, NJ (United States). Dept. of Chemistry and Chemical Biology
  2. Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0001780; SC0008640
Type:
Published Article
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 119; Journal Issue: 46; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Research Org:
Rutgers Univ., Piscataway, NJ (United States); Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1248414
Alternate Identifier(s):
OSTI ID: 1434921

Wu, Boning, Liang, Min, Maroncelli, Mark, and Castner, Edward W. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids. United States: N. p., Web. doi:10.1021/acs.jpcb.5b09216.
Wu, Boning, Liang, Min, Maroncelli, Mark, & Castner, Edward W. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids. United States. doi:10.1021/acs.jpcb.5b09216.
Wu, Boning, Liang, Min, Maroncelli, Mark, and Castner, Edward W. 2015. "Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids". United States. doi:10.1021/acs.jpcb.5b09216.
@article{osti_1248414,
title = {Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids},
author = {Wu, Boning and Liang, Min and Maroncelli, Mark and Castner, Edward W.},
abstractNote = {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 tetracyano-borate. 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. Finally, 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.},
doi = {10.1021/acs.jpcb.5b09216},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 46,
volume = 119,
place = {United States},
year = {2015},
month = {10}
}