The application of ionic liquids (ILs) has grown enormously, from their use as simple solvents, catalysts, media in separation science, or electrolytes to that as task-specific, tunable molecular machines with appropriate properties. A thorough understanding of these properties and structure–property relationships is needed to fully exploit their potential, open new directions in IL-based research and, finally, properly implement the appropriate applications. In this work, we investigated the structure–properties relationships of a series of alkyltriethylammonium bis(trifluoromethanesulfonyl)imide [TEA-R][TFSI] ionic liquids in relation to their thermal behavior, structure organization, and self-diffusion coefficients in the bulk state using DSC, FT-IR, SAXS, and NMR diffusometry techniques. The phase transition temperatures were determined, indicating alkyl chain dependency. Fourier-transformed infrared spectroscopy studies revealed the structuration of the ionic liquids along with alkyl chain elongation. SAXS experiments clearly demonstrated the existence of polar/non-polar domains. The alkyl chain length influenced the expansion of the non-polar domains, leading to the expansion between cation heads in polar regions of the structured IL. ¹H NMR self-diffusion coefficients indicated that alkyl chain elongation generally caused the lowering of the self-diffusion coefficients. Moreover, we show that the diffusion of anions and cations of ILs is similar, even though they vary in their size.

¹H and ¹⁹F spin-lattice relaxation experiments have been performed for a series of ionic liquids sharing the same anion: bis(trifluoromethanesulfonyl)imide but including cations of different alkyl chain lengths: butyltriethylammonium, triethyloctylammonium, dodecyltriethylammo-nium and hexadecyltriethylammonium. The studies have been carried out in the temperature range from 383 to 108 K at the resonance frequency of 200 MHz (for ¹H). A quantitative analysis of the relaxation data has revealed two dynamical processes for both kinds of ions. The dynamics have been successfully modeled in terms of the Arrhenius law. The timescales of the dynamical processes and their temperature evolution have been discussed in detail, depending on the structure of the cation.