Thiocyanate as a local probe of ultrafast structure and dynamics in imidazolium-based ionic liquids: water-induced heterogeneity and cation-induced ion pairing.
Ultrafast two-dimensional infrared spectroscopy (2D-IR) of thiocyanate ([SCN]−) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]) and 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1C1(2)im][NTf2]) ionic liquids probes local structure and dynamics as a function of the water content, solute counterion, and solute concentration. The 2D-IR spectra of the water-saturated ionic liquids resolve two distinct kinds of dynamics. This dynamical heterogeneity is explained as two subensembles, one with and one without a water molecule in the first solvation shell. When the countercation is K+, ion pairs between K+ and [SCN]− that persist for >100 ps are detected by long-lasting vibrational frequency correlations. The observed dynamics are invariant to [SCN]− concentration, which indicates that the [SCN]− does not cluster in ionic liquid solution. Taken together, these results are consistent with a picture of thiocyanate as a local probe that can interrogate ultrafast structure and dynamics at a small spatial scale in ionic liquids.
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260, United States.
Zhe
Z
Ren
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260, United States.
Thomas
T
Brinzer
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260, United States.
Samrat
S
Dutta
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260, United States.
Sean
S
Garrett-Roe