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We used a combination of theoretical and experimental methods to derive the spectroscopic properties of imidazolium-based ionic liquids. Vibrational frequencies, NMR chemical shifts, and quadrupole coupling constants react in comparable manner to changes in the chemical environment. This suggests that both the IR and the NMR spectroscopic properties reflect a similar type of electronic perturbation caused by hydrogen bonding. These relationships of the spectroscopic properties provide detailed information about structural complexes and may thus serve as good indicators of ion-pair formation. They also help to decide which spectroscopic tool is the most sensitive for investigating molecular interactions. The measurement of only one spectroscopic property allows the prediction of other properties that cannot be so easily measured. In some cases, this is the only way to obtain reliable coupling constants for deriving molecular correlation times from macroscopic NMR relaxation times, thus opening a new path for studying structure-dynamics relations in ionic liquids.

We have used 2H magnetic relaxation to study the single-particle reorientation of the 1-ethyl-3-methylimidazolium ([emim]+) ion in two prototypical low-viscosity ionic liquids comprising the bis(trifluoromethylsulfonyl)imide ([Tf2N]−) and dicyanimide ([(CN)2N]−) anions. Hydrodynamic analysis reveals extremely low (‘subslip’) coupling factors not captured by existing theories. Comparison with the microwave dielectric spectrum of [emim][Tf2N] shows that the dominant diffusive component of the dielectric response can be rationalized by single-particle reorientation of the cations.

The formation, stabilisation and reactivity of contact ion pairs of non-protic imidazolium ionic liquids (ILs) in solution are conceptualized in light of selected experimental evidence as well theoretical calculations reported mainly in the last ten years. Electric conductivity, NMR, ESI-MS and IR data as well as theoretical calculations support not only the formation of contact ion pairs in solution, but also the presence of larger ionic and neutral aggregates even when dissolved in solvents with relatively high dielectric constants, such as acetonitrile and DMSO. The presence of larger imidazolium supramolecular aggregates is favoured at higher salt concentrations in solvents of low dielectric constant for ILs that contain shorter N-alkyl side chains associated with anions of low coordination ability. The stability and reactivity of neutral contact species are also dependent on the nature of the anion, imidazolium substituents, and are more abundant in ILs containing strong coordinating anions, in particular those that can form charge transfer complexes with the imidazolium cation. Finally, some ILs display reactivities as contact ion pairs rather than solvent-separated ions.

With a combination of FTIR and ab initio calculations we studied the structure of water molecules confined in ionic liquids (ILs). Most of the single water molecules are H-bonded in double donor (DD) configurations either to one anion or to two anions in a 1 : 2 complex. We show that the vibrational stretching modes of such water molecules can be used as sensitive probes for the polarity of the ILs, expressed through dielectric constants. We apply our method to imidazolium salts of the third and fourth generation. We discuss the anion- and cation-dependence and compare our results with other polarity parameters.

Similarities and differences: Far-infrared spectra of protic ionic liquids could be assigned to intermolecular bending and stretching modes of hydrogen bonds. The characteristics of the low-frequency spectra resemble those of water. Both liquids form three-dimensional network structures, but only water is capable of building tetrahedral configurations. EAN: ethylammonium nitrate, PAN: propylammonium nitrate, DMAN: dimethylammonium nitrate.

Cohesion energies determine the phase behavior of materials. The understanding of interaction energies is in particular interesting for ionic liquids. Here we show experimentally that, in accord with theoretical work, the intermolecular cation-anion interactions in ionic liquids can be detected by far FTIR spectroscopy. The measured vibrational bands of aprotic and protic ionic liquids in the low-frequency range can be referred to the interaction strength between cations and anions in various combinations. It can be shown by DFT B3LYP calculations that these interactions are described by characteristic ratios between Coulomb forces and hydrogen bonds. These ratios can be tuned towards increasing hydrogen bond contributions which is reflected in important macroscopic properties of ionic liquids such as enthalpies of vaporization and viscosities. This opens a new path for tuning the desired properties of this new class of material.