title: Nonstoichiometric, Protic Azolium Azolate Ionic Liquids Provide Unique Environments for N-Donor Coordination Chemistry.
abstract: 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 H2 O, 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).
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35401 (USA).
authors.forename: Steven P
authors.initials: SP
authors.lastname: Kelley
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35401 (USA).
authors.forename: Joseph S
authors.initials: JS
authors.lastname: Nuss
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35401 (USA). robin.rogers@mcgill.ca.|Department of Chemistry, McGill University, 801 Sherbrooke St. West, Montreal, QC H3A 0B8 (Canada). robin.rogers@mcgill.ca.
authors.forename: Robin D
authors.initials: RD
authors.lastname: Rogers
keywords: N ligands; copper; crystal engineering; ionic liquids; zinc