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Title: The influence of mesoscopic confinement on the dynamics of imidazolium-based room temperature ionic liquids in polyether sulfone membranes

Abstract

The structural dynamics of a series of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C nmimNTf 2, n = 2, 4, 6, 10: ethyl—Emim; butyl—Bmim; hexyl—Hmim; decyl—Dmim) room temperature ionic liquids confined in the pores of polyether sulfone (PES 200) membranes with an average pore size of ~350 nm and in the bulk liquids were studied. Time correlated single photon counting measurements of the fluorescence of the fluorophore coumarin 153 (C153) were used to observe the time-dependent Stokes shift (solvation dynamics). The solvation dynamics of C153 in the ionic liquids are multiexponential decays. The multiexponential functional form of the decays was confirmed as the slowest decay component of each bulk liquid matches the slowest component of the liquid dynamics measured by optical heterodyne-detected optical Kerr effect (OHD-OKE) experiments, which is single exponential. The fact that the slowest component of the Stokes shift matches the OHD-OKE data in all four liquids identifies this component of the solvation dynamics as arising from the complete structural randomization of the liquids. Although the pores in the PES membranes are large, confinement on the mesoscopic length scale results in substantial slowing of the dynamics, a factor of ~4, for EmimNTf2, with the effect decreasing as the chain length increases. Bymore » DmimNTf 2, the dynamics are virtually indistinguishable from those in the bulk liquid. The rotation relaxation of C153 in the four bulk liquids was also measured and showed strong coupling between the C153 probe and its environment.« less

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Stanford Univ., CA (United States)
Publication Date:
Research Org.:
Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1540127
Alternate Identifier(s):
OSTI ID: 1420663
Grant/Contract Number:  
[FG03-84ER13251]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 147; Journal Issue: 19]; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Thomaz, Joseph E., Bailey, Heather E., and Fayer, Michael D. The influence of mesoscopic confinement on the dynamics of imidazolium-based room temperature ionic liquids in polyether sulfone membranes. United States: N. p., 2017. Web. doi:10.1063/1.5003036.
Thomaz, Joseph E., Bailey, Heather E., & Fayer, Michael D. The influence of mesoscopic confinement on the dynamics of imidazolium-based room temperature ionic liquids in polyether sulfone membranes. United States. doi:10.1063/1.5003036.
Thomaz, Joseph E., Bailey, Heather E., and Fayer, Michael D. Wed . "The influence of mesoscopic confinement on the dynamics of imidazolium-based room temperature ionic liquids in polyether sulfone membranes". United States. doi:10.1063/1.5003036. https://www.osti.gov/servlets/purl/1540127.
@article{osti_1540127,
title = {The influence of mesoscopic confinement on the dynamics of imidazolium-based room temperature ionic liquids in polyether sulfone membranes},
author = {Thomaz, Joseph E. and Bailey, Heather E. and Fayer, Michael D.},
abstractNote = {The structural dynamics of a series of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (CnmimNTf2, n = 2, 4, 6, 10: ethyl—Emim; butyl—Bmim; hexyl—Hmim; decyl—Dmim) room temperature ionic liquids confined in the pores of polyether sulfone (PES 200) membranes with an average pore size of ~350 nm and in the bulk liquids were studied. Time correlated single photon counting measurements of the fluorescence of the fluorophore coumarin 153 (C153) were used to observe the time-dependent Stokes shift (solvation dynamics). The solvation dynamics of C153 in the ionic liquids are multiexponential decays. The multiexponential functional form of the decays was confirmed as the slowest decay component of each bulk liquid matches the slowest component of the liquid dynamics measured by optical heterodyne-detected optical Kerr effect (OHD-OKE) experiments, which is single exponential. The fact that the slowest component of the Stokes shift matches the OHD-OKE data in all four liquids identifies this component of the solvation dynamics as arising from the complete structural randomization of the liquids. Although the pores in the PES membranes are large, confinement on the mesoscopic length scale results in substantial slowing of the dynamics, a factor of ~4, for EmimNTf2, with the effect decreasing as the chain length increases. By DmimNTf2, the dynamics are virtually indistinguishable from those in the bulk liquid. The rotation relaxation of C153 in the four bulk liquids was also measured and showed strong coupling between the C153 probe and its environment.},
doi = {10.1063/1.5003036},
journal = {Journal of Chemical Physics},
number = [19],
volume = [147],
place = {United States},
year = {2017},
month = {11}
}

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