Structural Anomalies in Ionic Liquids near the Glass Transition Revealed by Pulse EPR

Unusual physical and chemical properties of ionic liquids (ILs) open up prospects for various applications. We report the first observation of density/rigidity heterogeneities in a series of ILs near the glass transition temperature ( T_g) by means of pulse electron paramagnetic resonance (EPR). Unprecedented suppression of molecular mobility is evidenced near the glass transition, which is assigned to unusual structural rearrangements of ILs on the nanometer scale. Indeed, pulse and continuous wave EPR clearly indicate the occurrence of heterogeneities near T_g, which exist in a rather broad temperature range of ∼50 K. The two types of local environments are evidenced, being drastically different by their stiffness. The more rigid one suppresses molecular mobility, whereas the softer one instead promotes diffusive molecular rotation. Such properties of ILs near T_g are of general importance; moreover, the observed density/rigidity heterogeneities controlled by temperature might be considered as a new type of tunable reaction nanoenvironment.