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This content will become publicly available on January 29, 2019

Title: Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution. The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.
Authors:
ORCiD logo [1] ;  [1] ;  [2] ;  [3] ;  [4] ; ORCiD logo [2] ; ORCiD logo [5] ; ORCiD logo [1]
  1. Rutgers Univ., Piscataway, NJ (United States). Dept. of Chemistry and Chemical Biology
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  3. The Graduate Center of CUNY, New York, NY (United States); Hunter College, New York, NY (United States)
  4. Queensborough Community College, Bayside, NY (United States). Dept. of Chemistry
  5. Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemistry
Publication Date:
Report Number(s):
BNL-203219-2018-JAAM
Journal ID: ISSN 1520-6106
Grant/Contract Number:
SC0012704; SC0001780; SC0008640
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 122; Journal Issue: 8; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (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; ionic liquids
OSTI Identifier:
1425075