A Comparison of Electron-Transfer Dynamics inIonic Liquids and Neutral Solvents

F, Wishart J; Lee, H Y; Issa, J B; Isied, S S; Pan, Y; Hussey, C L; Lee, K S

Title: A Comparison of Electron-Transfer Dynamics inIonic Liquids and Neutral Solvents

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Abstract

The effect of ionic liquids on photoinduced electron-transfer reactions in a donor-bridge-acceptor system is examined for two ionic liquid solvents, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and tributylmethylammonium bis(trifluoromethylsulfonyl)amide. The results are compared with those for the same system in methanol and acetonitrile solution. Electron-transfer rates were measured using time-resolved fluorescence quenching for the donor-bridge-acceptor system comprising a 1-N,1-N-dimethylbenzene-1,4-diamine donor, a proline bridge, and a coumarin 343 acceptor. The photoinduced electron-transfer processes are in the inverted regime (-{Delta}G > {lambda}) in all four solvents, with driving forces of -1.6 to -1.9 eV and estimated reorganization energies of about 1.0 eV. The observed electron-transfer kinetics have broadly distributed rates that are generally slower in the ionic liquids compared to the neutral solvents, which also have narrower rate distributions. To describe the broad distributions of electron-transfer kinetics, we use two different models: a distribution of exponential lifetimes and a discrete sum of exponential lifetimes. Analysis of the donor-acceptor electronic coupling shows that for ionic liquids this intramolecular electron-transfer reaction should be treated using a solvent-controlled electron-transfer model.

Authors:: F, Wishart J; Lee, H Y; Issa, J B; Isied, S S; Pan, Y; Hussey, C L; Lee, K S

Publication Date:: Thu Mar 01 00:00:00 EST 2012

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE SC OFFICE OF SCIENCE (SC)

OSTI Identifier:: 1044019

Report Number(s):: BNL-96369-2012-JA
Journal ID: ISSN 1932-7447; R&D Project: CO-004; KC0301010; TRN: US201214%%274

DOE Contract Number:: DE-AC02-98CH10886

Resource Type:: Journal Article

Journal Name:: Journal of Physical Chemistry C

Additional Journal Information:: Journal Volume: 116; Journal Issue: 8; Journal ID: ISSN 1932-7447

Country of Publication:: United States

Language:: English

Subject:: 10 SYNTHETIC FUELS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETONITRILE; COUMARIN; DISTRIBUTION; ELECTRON TRANSFER; FLUORESCENCE; KINETICS; METHANOL; MOLTEN SALTS; PROLINE; QUENCHING; SOLVENTS

Citation Formats


                    F, Wishart J, Lee, H Y, Issa, J B, Isied, S S, Castner, Jr., E.W., Pan, Y, Hussey, C L, and Lee, K S. A Comparison of Electron-Transfer Dynamics inIonic Liquids and Neutral Solvents.  United States: N. p., 2012. 
        Web.

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                    F, Wishart J, Lee, H Y, Issa, J B, Isied, S S, Castner, Jr., E.W., Pan, Y, Hussey, C L, & Lee, K S. A Comparison of Electron-Transfer Dynamics inIonic Liquids and Neutral Solvents.  United States.

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                    F, Wishart J, Lee, H Y, Issa, J B, Isied, S S, Castner, Jr., E.W., Pan, Y, Hussey, C L, and Lee, K S. 2012.  
        "A Comparison of Electron-Transfer Dynamics inIonic Liquids and Neutral Solvents".  United States.

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@article{osti_1044019,

  title        = {A Comparison of Electron-Transfer Dynamics inIonic Liquids and Neutral Solvents},

  author       = {F, Wishart J and Lee, H Y and Issa, J B and Isied, S S and Castner, Jr., E.W. and Pan, Y and Hussey, C L and Lee, K S},

  abstractNote = {The effect of ionic liquids on photoinduced electron-transfer reactions in a donor-bridge-acceptor system is examined for two ionic liquid solvents, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and tributylmethylammonium bis(trifluoromethylsulfonyl)amide. The results are compared with those for the same system in methanol and acetonitrile solution. Electron-transfer rates were measured using time-resolved fluorescence quenching for the donor-bridge-acceptor system comprising a 1-N,1-N-dimethylbenzene-1,4-diamine donor, a proline bridge, and a coumarin 343 acceptor. The photoinduced electron-transfer processes are in the inverted regime (-{Delta}G > {lambda}) in all four solvents, with driving forces of -1.6 to -1.9 eV and estimated reorganization energies of about 1.0 eV. The observed electron-transfer kinetics have broadly distributed rates that are generally slower in the ionic liquids compared to the neutral solvents, which also have narrower rate distributions. To describe the broad distributions of electron-transfer kinetics, we use two different models: a distribution of exponential lifetimes and a discrete sum of exponential lifetimes. Analysis of the donor-acceptor electronic coupling shows that for ionic liquids this intramolecular electron-transfer reaction should be treated using a solvent-controlled electron-transfer model.},

  doi          = {},

  url          = {https://www.osti.gov/biblio/1044019},
  journal      = {Journal of Physical Chemistry C},

  issn         = {1932-7447},

  number       = 8,

  volume       = 116,

  place        = {United States},

  year         = {Thu Mar 01 00:00:00 EST 2012},

  month        = {Thu Mar 01 00:00:00 EST 2012}

}

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