Peculiar Behavior of Azolium Azolate Energetic Ionic Liquids

We present studies of molecular dynamics and interactions in azolium azolate energetic ionic liquids (ILs) by utilizing a variety of physical methods. We observe peculiar rheological behavior for these ILs, which deviates from the one expected for molecular glass-formers. Major peculiarities include high elasticity in the low-frequency zone, peculiar van Gurp plots, and failure of time temperature superposition. We attribute these peculiarities to specific interactions in the nitrogen-rich planar rings of azolate ILs. X-ray scattering measurements reveal a nanometer ordered organization in azolium azolates. High values of Kamlet-Taft polarity parameters indicate high probability and strength of hydrogen bond interactions in azolate ILs. This conclusion is also supported by ab initio calculations. Our next effort is to break/enhance existing interactions in nitrogen-rich Its by adding a H-acceptor. This will allow better understanding of the nature of interactions in azolium azolates and eventually their control.