Hydrogen bonding in ionic liquids probed by linear and nonlinear vibrational spectroscopy

Three imidazolium-based ionic liquids of the type [C(n)mim][NTf2] with different alkyl chain lengths (n = 1, 2 and 8) at the first position of the imidazolium ring were studied applying infrared, linear Raman and multiplex coherent anti-Stokes Raman scattering spectroscopy. The focus has been on the CH-stretching region of the imidazolium ring, which is supposed to carry information about a possible hydrogen bonding network in the ionic liquid. The measurements are compared with calculations of the corresponding anharmonic vibrational spectra for a cluster of [C(2)mim][NTf2] consisting of four ion pairs. The results support the hypothesis of weak hydrogen bonding involving the C(4)-H and C(5)-H groups and somewhat stronger hydrogen bonds of the C(2)-H groups.