Azolate Anions in Ionic Liquids: Promising and Under-Utilized Components of the Ionic Liquid Toolbox

Owing to their ease of synthesis, diffuse positive charge, and chemical stability, 1-alkyl-3-methylimidazolium cations (i.e., C_nmim]⁺) are one of the most routinely utilized and historically important components in ionic liquid (IL) chemistry. However, while this is a routinely encountered member of the IL family as cations, relatively few workers have explored the versatile chemistry of azoles to allow their use as an anionic component in ILs, as azolates. Azolate anions possess many of the desired properties for IL formation, including a diffuse ionic charge, tailorable asymmetry, and synthetic flexibility, with the added advantages of not relying on halogen atoms for electron-withdrawing effects, as is commonly encountered with IL anions such as hexafluorophosphate. This review explores the 122 azolate-containing ILs known in the literature (prepared from only 39 disparate azolate anions), with a view to highlighting not only their demonstrated utility as an IL component, but the ways in which the larger scientific community may utilize their advantageous properties for new tailored materials.