Abstract
New 1:2 liquid crystalline supramolecular H-bonded complexes (SMHBCs) were synthesized through double H-bond interactions between 4-(nicotinoyloxy) phenyl nicotinate as the base component and two molecules of 4-n-alkoxybenzoic acid (An). The base component was expected to be in two conformers according to the orientation of the N atom and the carboxylate group,
syn
conformer (
I
) and
anti
-conformer (
II
). DFT calculations revealed that only one of the two possible conformers of
I
exists, and the addition of the two molecules of the alkoxy acids (
A
n
) did not affect its conformation. The mesomorphic properties of all of the prepared complexes (
I
/
A
n
), bearing different terminal flexible alkoxy chains were investigated, and the formation of the H-bonds were confirmed by differential scanning calorimetry (DSC), and the phases were identified by polarized optical microscopy (POM), and FT-IR spectroscopy. Highly thermally stable mesophases possessing broad temperature ranges were observed for all investigated complexes compared to their individual components. Depending on the length of the terminal flexible alkoxy chain, the prepared SMHBCs were shown to exhibit di- or tri-morphic enantiotropic mesophases. The effect of replacing one of the –COO– connecting units by an azo group (-N=N-) in the basic molecule (
I
), on the mesomorphic properties has been investigated experimentally (
via
DSC) and theoretically (
via
DFT). The DFT calculations revealed that the polarizability, the dipole moment, and the aspect ratio of the investigated SMHBCs are lower than those of their corresponding ester/azo analogs. All these factors rationalize the enhanced smectic mesophase ranges of the complexes compared with those of the ester/azo analogs. The high aspect ratios and dipole moments of the SMHBCs of the azo derivative enforces the lateral intermolecular attraction that permits the formation of the more ordered smectic C mesophase with respect to the enhanced polymorphic mesophases of the diester derivative.