Nuclear Magnetic Relaxation and Diffusion Study of the Ionic Liquids 1-ethyl- and 1-butyl-3-methylimidazolium bis (trifluoromethylsulphonyl)imide Confined in Porous Glass.

The molecular dynamics of the room-temperature ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethylsulphonyl)imide (Bmim Tf2N) confined in porous glass is studied by NMR relaxometry and diffusometry, and is compared to its bulk dynamics over a wide temperature range. The molecular reorientation processes for anions and cations alike are found to be significantly affected by the presence of the glass interface at high temperatures. In this respect, the ionic liquid behaves similar to polar liquids where proton NMR relaxation is governed by reorientations mediated by translational displacements (RMTD). This process becomes less significant towards lower temperatures when the characteristic translational correlation times of the ions approach a timescale comparable to the RMTD process, and the relaxation dispersions in bulk and in confinement become similar below a temperature corresponding to about 1.2 Tg , a value where the onset of dynamic heterogeneity has been observed before. The self-diffusion coefficient, on the other hand, is found to be strongly reduced compared to bulk within the accessible temperature range of 248 K and above, and is significantly slower than expected from the tortuosity effect, suggesting that ion-surface interactions affect the macroscopic properties.