Computational Study of Monosubstituted Azo(tetrazolepentazolium)-Based Ionic Dimers.

The structures of monosubstituted azo(tetrazolepentazolium) cations (N11CHR(+)), oxygen-rich anions such as N(NO2)2(-), NO3(-), and ClO4(-), and the corresponding ion pairs are investigated using ab initio quantum chemistry calculations. The substituents (R) used are H, F, CH3, CN, NH2, OH, OCH3, N3, NF2, and C2H3. The stability of the protonated cation is explored by examining the decomposition pathway of the protonated cation (N11CH2(+)) to yield molecular N2 fragments. The heats of formation of these cations, which are based on isodesmic (bond type conserving) reactions, are dependent on the nature of the substituents. Ionic dimer structures are obtained, but side reactions including proton transfer, binding, and hydrogen bonding are observed in the gas phase. Implicit solvation studies are performed to determine the solution properties of the ion pairs.