TY - JOUR
T1 - Photoinduced Bimolecular Electron Transfer in Ionic Liquids
T2 - Cationic Electron Donors
AU - Wu, Boning
AU - Liang, Min
AU - Zmich, Nicole
AU - Hatcher, Jasmine
AU - Lall-Ramnarine, Sharon I.
AU - Wishart, James F.
AU - Maroncelli, Mark
AU - Castner, Edward W.
N1 - Funding Information:
This research was funded by a collaborative grant from the U.S. Department of Energy, Office of Basic Sciences, Division of Chemical Sciences, Geosciences, under contract nos. DESC0001780 (Rutgers), DE-SC0008640 (Penn State), and DESC0012704 (BNL: J.F.W., N.Z., and J.H.). The authors thank Prof. Dr. Eric Vauthey for the gifts of TrCNA and TCNA fluorophores. At Rutgers, they thank Letao Yang for help with cyclic voltammetry experiments, Prof. KiBum Lee for loan of the BASi electrochemical analyzer, and Dr. Nagarajan Murali for assistance with the PG-SE NMR diffusivity measurements.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/3/1
Y1 - 2018/3/1
N2 - 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 ]. Herein, 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. 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.
AB - 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 ]. Herein, 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. 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.
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U2 - 10.1021/acs.jpcb.7b12542
DO - 10.1021/acs.jpcb.7b12542
M3 - Article
C2 - 29377698
AN - SCOPUS:85042760734
SN - 1520-6106
VL - 122
SP - 2379
EP - 2388
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 8
ER -