Nonstoichiometric,Protic Azolium Azolate Ionic Liquids Provide Unique Environments for N‐Donor Coordination Chemistry

Here we demonstrate that neat reactions of amphoteric azoles with more basic azoles give a family of finely tunable, nonstoichiometric liquids which are useful for N‐donor coordination chemistry. Reacting 4,5‐dicyanoimidazole (4,5‐DCNIm) with 1‐methylimidazole (1‐mim) gives new compounds with composition‐dependent speciation. Two crystalline compounds, a 1:1 protic salt, H(1‐mim)]4,5‐DCNIm], and a 1:2 salt co‐crystal, H(1‐mim)]4,5‐DCNIm]?4,5‐DCNIm, were isolated and structurally characterized, while differential scanning calorimetry revealed both suppression of crystallization and the presence of neutral and anionic species in the melt. Reactions of Cu(NO₃)₂?2.5 H₂O, CuO, and ZnO with the neat 2:1 1‐mim/4,5‐DCNIm melt resulted in the isolation of entirely N‐donor ligated complexes of the formula M(4,5‐DCNIm)₂(1‐mim)₄ (M=Cu, Zn).