Ion-Pairing Assemblies of π-Electronic Anions Formed by Intramolecular Hydrogen Bonding

-Extended nitro-substituted dipyrrolylphenol derivatives were synthesized, and upon deprotonation they provided -electronic anions stabilized by hydrogen bonding between the phenolate (phenoxide) moiety and the pyrrole NH group. Ion-pairing assemblies of the deprotonated anions were formed in the solid state and as mesophases. In the solid state, the extended plane was found to be more suitable to form charge-by-charge assemblies in combination with tetraalkylammonium cations with highly anisotropic orientations as a result of efficient stacking. The mesophase also included a charge-by-charge assembly comprising the deprotonated anion bearing aliphatic chains, as revealed by synchrotron X-ray diffraction analysis.