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

Thomaz, Joseph E.; Bailey, Heather E.; Fayer, Michael D.

doi:10.1063/1.5003036

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

Journal Article · Wed Nov 15 00:00:00 EST 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5003036· OSTI ID:1540127

Thomaz, Joseph E. ^[1]; Bailey, Heather E. ^[1];

^[1]

Stanford Univ., CA (United States)

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 membranes (PES 200) 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.

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Research Organization:: Stanford Univ., CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: FG03-84ER13251; FG02-84ER13251

OSTI ID:: 1540127

Alternate ID(s):: OSTI ID: 1420663; OSTI ID: 1797293

Journal Information:: Journal of Chemical Physics, Vol. 147, Issue 19; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 18 works

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

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