Clusters of the Ionic Liquid 1-Hydroxyethyl-3-methylimidazolium Picrate: From Theoretical Prediction in the Gas Phase to Experimental Evidence in the Solid State

Interonic interactions determine the macroscopic properties of ionic liquids (ILs). Hence, unravelling the relationships between the microscopic and macroscopic scales is key for rational design. Combining density functional theory (DFT) calculations of isolated ion pairs and vibrational spectroscopy of the condensed phase (fluid or solid) has become a very common approach. In the present work, we make a step towards understanding how the physicochemical effects in small gas phase clusters of a hydroxyl functionalized imidazolium-picrate IL relate with the molecular structure and interactions of the corresponding solid material taking 1-hydroxyethyl-3-methylimidazolium picrate, C(2)OHmimPic, as an example. In the isolated ion pair, strong alkyl-OH center dot center dot center dot Pic hydrogen bonding interactions are found rather than the commonly observed hydrogen bonding interactions at the slightly acidic C(2)-H site of the imidazolium ring. However, this part of the cation plays an important role when clusters of ion pairs in the gas phase and inside a crystal lattice are considered. For example, in the dimeric ion-pair cluster, one centre (O*) with two interaction sites (C(2)-H-O* and alkyl OH-Pic) is observed. This configuration is suggested by single crystal X-ray diffraction (XRD), vibrational spectroscopy, and the dispersion-corrected DFT calculations. Hence, the study provides evidence for the appearance of theoretical gas phase clusters in an actual solidified ionic liquid. This ion pair dimer formation may be a general behavior of hydroxyl functionalized imidazolium ILs, but further research is needed to draw a final conclusion. Moreover, the Raman spectra confirm the exclusive gauche conformation of the hyroxyl functionalized alkyl chain.