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Measurements of the Complete Solvation Response in Ionic Liquids
Abstract
Dynamic Stokes shift measurements of the solvatochromic probe trans-4-dimethylamino-4'-cyanostilbene were used to measure the solvation response of five imidazolium and one pyrrolidinium ionic liquid at 25 degrees C. The Kerr-gated emission and time-correlated single-photon-counting techniques were used to measure spectral dynamics occurring over the time ranges of 100 fs-200 ps and 50 ps-5 ns, respectively, and a combination of data sets from these two techniques enabled observation of the complete solvation response. Observed response functions were found to be biphasic, consisting of a sub-picosecond component of modest (10-20%) amplitude and a dominant slower component relaxing over times of a few picoseconds to several nanoseconds. The faster component could be correlated to inertial characteristics of the constituent ions, and the slower component to solvent viscosity. Dielectric continuum calculations of the sort previously used to predict solvation dynamics in dipolar liquids were shown to work poorly for predicting the response in these ionic liquids.
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Citations
Cites
Ionic liquids: solvent properties and organic reactivity
Chiappe, C., & Pieraccini, D. (2005) · Journal of Physical Organic Chemistry · doi:10.1002/poc.863 · Cited by 1,169
Cited by
Deep eutectic solvents: A review of fundamentals and applications
Hansen, B. B., Spittle, S., Chen, B., Poe, D., Zhang, Y., Klein, J. M., Horton, A., Adhikari, L., Zelovich, T., Doherty, B. W., et al. (2021) · Chemical Reviews · doi:10.1021/acs.chemrev.0c00385 · Cited by 3,422
Self-citationUnderstanding Ionic Liquids at the Molecular Level: Facts, Problems, and Controversies
Weingärtner, H. (2008) · Angewandte Chemie International Edition · doi:10.1002/anie.200604951 · Cited by 1,543
Jin, H., O'Hare, B., Dong, J., Arzhantsev, S., Baker, G. A., Wishart, J. F., Benesi, A. J., & Maroncelli, M. (2008) · The Journal of Physical Chemistry B · doi:10.1021/jp076462h · Cited by 422
Self-citationCastner, E. W., & Wishart, J. F. (2010) · The Journal of Chemical Physics · doi:10.1063/1.3373178 · Cited by 398
Jin, H., Baker, G. A., Arzhantsev, S., Dong, J., & Maroncelli, M. (2007) · The Journal of Physical Chemistry B · doi:10.1021/jp070923h · Cited by 310
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Metadata
- Authors
- Arzhantsev, S., Jin, H., Baker, G. A., & Maroncelli, M.
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 2007-02-24
- Volume
- 111
- Issue
- 18
- Pages
- 4978-4989
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- OpenAlex
- W2066972471
- Cited by
- 222
- References
- 1
- FWCI
- 12.02
- Type
- journal article
- Language
- en
- Open access
- closed
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- Arzhantsev, S., Jin, H., Baker, G. A., & Maroncelli, M. (2007). Measurements of the Complete Solvation Response in Ionic Liquids. The Journal of Physical Chemistry B. https://doi.org/10.1021/jp067273m
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