Kinetics and Energetics of Thermal Cis-Trans Isomerization of a Resonance-Activated Azobenzene in BMIM-Based Ionic Liquids for PF₆/Tf₂N Comparison.

BMIM PF₆ (1-butyl-3-methylimidazolium hexafluorophosphate) and BMIM Tf₂N (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) are two room-temperature ionic liquids widely employed and investigated as reaction media. Despite the presence of the same imidazolium ring in their structure they are different in many chemical and physical properties due to the nature of the anions. The thermal isomerization of an electronically activated azobenzene have been used as reaction model to compare the behavior of PF₆ and Tf₂N. Rotation is the mechanism by which the investigated azobenzene is converted into the isomer spontaneously in the dark both in BMIM PF₆ and in BMIM Tf₂N. The kinetic rate constants of the process have been determined at different temperatures and the activation energies of the reaction have been calculated according to the Arrhenius and Eyring equations. The results presented herein highlight different solute-solvent interactions involving the PF₆ and Tf₂N anions during the isomerization.