Evidence of C--F-P and aromatic π--F-P weak interactions in imidazolium ionic liquids and its consequences

A simple change from alkyl group to alkene in side chain of imidazolium cation with same anion resulted in a drastic impact on physical properties (e.g., melting point) from bmimPF₆ IL to cmimPF₆ IL. The underlying reasons have been elucidated by structural and interaction studies with the help of DSC, SCXRD, vibrational and multi-nuclear NMR spectroscopic techniques. Experiments reveal existence of new weak interactions involving the carbon and π cloud of the imidazolium aromatic ring with fluoride of PF₆ anion (i.e., C₂--F-P and π--F-P) in cmimPF₆ but are absent in structurally similar prototype IL, bmimPF₆. Though weak, these interactions helped to form ladder type supramolecular arrangement, resulting in quite high melting point for cmimPF₆ IL compared to bmimPF₆ IL. These findings emphasize that an IL system can behave uniquely because of the existence of uncommon weak interactions.