Ionic Liquids Based on Azolate Anions

Compartmentalized molecular level design of new energetic materials based on energetic azolate anions allows for the examination of the effects of both cation and anion on the physiochemical properties of ionic liquids. Thirty one novel salts were synthesized by pairing diverse cations (tetraphenylphosphonium, ethyltriphenylphosphonium, N‐phenyl pyridinium, 1‐butyl‐3‐methylimidazolium, tetramethyl‐, tetraethyl‐, and tetrabutylammonium) with azolate anions (5‐nitrobenzimidazolate, 5‐nitrobenzotriazolate, 3,5‐dinitro‐1,2,4‐triazolate, 2,4‐dinitroimidazolate, 4‐nitro‐1,2,3‐triazolate, 4,5‐dinitroimidazolate, 4,5‐dicyanoimidazolate, 4‐nitroimidazolate, and tetrazolate). These salts have been characterized by DSC, TGA, and single crystal X‐ray crystallography. The azolates in general are surprisingly stable in the systems explored. Ionic liquids were obtained with all combinations of the 1‐butyl‐3‐methylimidazolium cation and the heterocyclic azolate anions studied, and with several combinations of tetraethyl‐ or tetrabutylammonium cations and the azolate anions. Favorable structure–property relationships were most often achieved when changing from 4‐ and 4,5‐disubstituted anions to 3,5‐ and 2,4‐disubstituted anions. The most promising anion for use in energetic ionic liquids of those studied here, was 3,5‐dinitro‐1,2,4‐triazolate, based on its contributions to the entire set of target properties.