Study of Mesomorphism Behavior and Protonation-Induced Emission of Symmetrical Benzalazines

Rod-shaped and polycatenar symmetric benzalazines with protonation-induced emission were synthesized, characterized, and studied for their thermal and optical behavior. Benzalazines lacking hydroxy groups at the ortho position did not show luminescence in the solid state or solution. In the presence of HCl (either in solution or vapor form) these compounds became good emitters. The protonation of azine nitrogen that may hinder the N-N bond rotation by intermolecular interactions toward aggregates provided an explanation for the emission characteristics observed. The protonation-induced emission was thermally reversible. A benzalazine derived from 4-alkoxysalicylaldehyde with AIE property was prepared. For this compound with ortho-OH groups, the optical properties were not affected by the presence of acidic media. It exhibited a stable SmC phase characterized by POM, DSC, and XRD. The luminescence capability of the molecular arrangement within the smectic phase was investigated. The intense yellow-green emission in the crystals decreased significantly at the phase transition due to the non-radiative decay that occurs with increasing temperature, and loss of intermolecular H-bonding which prevents molecular rotations in the crystal.