Spectroscopic determination of relative Brønsted acidity as a predictor of reactivity in aprotic ionic liquids.

A simple titration technique utilizing pyridine as a FTIR spectroscopy probe is demonstrated to successfully predict relative Brønsted acid-limited reaction rates in different ionic liquid (IL) environments. Relative acidity is shown to vary across three aprotic ILs in a manner that is specific to the particular acid-IL pairing.

Poly(dimethylsiloxane)-supported ionogels with a high ionic liquid loading.

The immiscibility of poly(dimethylsiloxane) (PDMS) and ionic liquids (ILs) was overcome to create PDMS-supported IL gels (ionogels) with IL loadings of up to 80% by mass through a simple sol-gel reaction at room temperature. By stirring a mixture of a functionalized PDMS oligomer, formic acid, and an IL (or lithium-in-IL solution), a resin was formed that could be cast to create a freestanding, flexible ionogel. PDMS-supported ionogels exhibited favorable ionic conductivity (ca. 3 mS cm(-1)) and excellent mechanical behavior (elastic modulus: ca. 60 kPa; fatigue life: >5000 cycles; mechanically stable at temperatures up to 200 °C). The activation energy of ionic conductivity was shown to be nearly identical for the ionogel and the neat IL, in contrast to ionogel systems wherein the scaffold material is miscible with the IL. This similarity indicates that IL/scaffold chemical interactions are key to the understanding of ionogel electrical performance, especially at elevated temperatures.