Ionic liquids formed with polycyano 1,1,3,3-tetracyanoallyl anions: substituent effects of anions on liquid properties.

A series of ionic liquids based on five kinds of polycyano 1,1,3,3-tetracyanoallyl anions with 2-substituents having different electron-withdrawing or -donating abilities were prepared. The influence of the chemical modification on their thermal properties, viscosity, ionic conductivity, ion association, and solvatochromic shifts was characterized and compared with the case of previously reported polycyano anions, N(CN)(2)(-) and C(CN)(3)(-). Among the 1-butyl-3-methylimidazolium (BMI) salts, cyano-substituted (i.e., 1,1,2,3,3-pentacyanoallyl anion) salt has the highest melting point (42 degrees C), possibly indicating the importance of high local symmetry over decreased interionic CN...cation interactions due to the limited electron densities on terminal nitrogens of the anions, predicted by ab initio calculations. In the liquid state, methoxy-substituted (i.e., 2-methoxy-1,1,3,3-tetracyanoallyl anion) salt has the highest fluidity and ionic conductivity, associated with the significant conformational degree of freedom in the methoxy group. Although the ion diffusivity has no definite correlation with the Hammett parameter of the substituents, the introduction of electron-withdrawing cyano or cyanomethyl (i.e., 2-cyanomethyl-1,1,3,3-tetracyanoallyl anion) groups leads to the decrease in the degree of ion association and solvent donor ability, which were manifested in the Walden rule deviation and solvatochromic shift, respectively.