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

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 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.

Authors:
 [1];  [1];  [2];  [1]
  1. Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road, Piscataway, New Jersey 08854, United States
  2. Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
Publication Date:
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)
OSTI Identifier:
1248414
Alternate Identifier(s):
OSTI ID: 1434921
Grant/Contract Number:  
SC0001780; SC0008640
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Volume: 119 Journal Issue: 46; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wu, Boning, Liang, Min, Maroncelli, Mark, and Castner, Jr., Edward W.. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids. United States: N. p., 2015. Web. https://doi.org/10.1021/acs.jpcb.5b09216.
Wu, Boning, Liang, Min, Maroncelli, Mark, & Castner, Jr., Edward W.. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids. United States. https://doi.org/10.1021/acs.jpcb.5b09216
Wu, Boning, Liang, Min, Maroncelli, Mark, and Castner, Jr., Edward W.. Mon . "Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids". United States. https://doi.org/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, Jr., 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 = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcb.5b09216

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