The Nature of Cation-Anion Interactions in Magnetic Ionic Liquids as Revealed Using High-Pressure Fourier Transform Infrared (FT-IR) Spectroscopy.

Magnetic ionic liquids are a group of magneto-responsive compounds that typically possess high ionic conductivities and low vapor pressures. In spite of the general interest in these materials, a number of questions concerning the fundamental interactions among the ions remain unanswered. We used vibrational spectroscopy to gain insight into the nature of these interactions. Intramolecular vibrational modes of the ions are quite sensitive to their local potential energy environments, which are ultimately defined by cation-anion coordination schemes present among the ions. Ambient pressure Fourier transform infrared (FT-IR) spectroscopy indicates comparable interaction motifs for 1-ethyl-3-methylimidazolium tetrachloroferrate(III), [emim]FeCl4, and 1-ethyl-3-methylimidazolium tetrabromoferrate(III), [emim]FeBr4, magnetic ionic liquids. However, the vibrational modes of [emim]FeCl4 generally occur at slightly higher frequencies than those of [emim]FeBr4. These differences reflect different interaction strengths between the [emim]+ cations and FeCl4- or FeBr4- anions. This conclusion is supported by gas-phase ab initio calculations of single [emim]FeCl4 and [emim]FeBr4 ion pairs that show longer C-H···Br-Fe interaction lengths compared to C-H···Cl-Fe. Although the IR spectra of [emim]FeCl4 and [emim]FeBr4 are comparable at ambient pressure, a different series of spectroscopic changes transpire when pressure is applied to these compounds. This suggests [emim]+ cations experience different types of interaction with the anions under high-pressure conditions. The pressure-dependent FT-IR spectra highlights the critical role ligands attached to the tetrahalogenoferrate(III) anions play in modulating cation-anion interactions in magnetic ionic liquids.