A new series of Schiff base liquid crystal have been prepared and studied. Schiff bases of p-alkyl aniline derivatives and 4-phenyl pyridine-4′-carbaldehyde were prepared. The terminal alkyl groups substituting aniline are of varied chain length, namely C8, C12 and C14. The structures of the compounds were elucidated by 1H NMR and 13C NMR. The mesomorphic thermal and optical characteristics of the samples were determined via differential thermal analysis (DSC) and polarization optical microscopy (POM). All compounds exhibit enantiotropic dimorphic mesophase behaviour, referred to as smectic X1 (SmX1) and smectic X2 (Sm A). Experimental results obtained for the mesophases were correlated with density functional theory (DFT) theoretical calculations. The results of the new series are further compared to two series of compounds bearing pyridine (two ring Schiff bases) and biphenyl, respectively, in their mesogens. The series of compounds of one pyridine ring are generally not mesomorphic. The results indicate that the alkyl chain length has a strong impact on the mesomorphic characteristics and thermal stabilities of the different mesophases. As a trend, the temperature ranges of both of smectic mesophases of all compounds are higher in new compounds bearing the 4-phenyl pyridine moiety. In addition, the total mesophase range is generally higher in the new compounds when compared to their biphenyl analogues. Finally, theoretical DFT calculations were performed to illustrate the experimental finding of the mesomorphic behaviour in terms of the molecular geometry and aromaticity, π–π stacking and LOL-π.

A series of new supramolecular three-ring bent-shape Schiff base liquid crystal (LC) complexes were prepared and studied. On one side, two alkoxy chain lengths of the carboxylic acids were used, namely eight and sixteen carbons. Moreover, on the other side, terminal small compact groups, which substituted aniline, with different polarities were utilized. Furthermore, the hydrogen-bonding interactions in the formed complexes were elucidated by Fourier-transform infrared (FT–IR) spectroscopy. The mesomorphic thermal and optical characteristics of the samples were determined by differential thermal analysis (DSC) and polarized optical microscopy (POM). The complexes exhibited enantiotropic and dimorphic mesophase behaviors. The results indicate that the polarity of the compact groups and the lengths of the alkoxy chains greatly impacted the mesomorphic characteristics and thermal stabilities of the mesophases. The observed values of the enthalpy changes (ΔH) associated with the crystalline smectic-A (T_Cr-SmA) transitions were extremely small compared with the conventional values that characterize supramolecular hydrogen-bonded liquid crystalline complexes. ΔH, which corresponded to the nematic isotropic transitions (T_N-I), varied from 0.13 to 9.54 kJ/mol depending mainly on the polarity of the groups that were para-attached to the aniline moiety. Finally, the theoretical results obtained by density functional theory (DFT) calculations were discussed. The DFT geometrical structures showed non-coplanar structures. The mesomorphic range was correlated with the calculated dipole moment, polarizability and the aspect ratios of the investigated compounds.

A series of non-symmetrical Schiff base liquid crystals were prepared and investigated. Schiff bases of p-alkyloxy aniline derivatives and 4-phenyl pyridine-4′-carbaldehyde were synthesized. The terminal alkoxy groups substituting aniline are of varied chain length, namely C6, C8, and C16. The structures of the compounds were confirmed via ¹H NMR and ¹³C NMR spectroscopy. Different mesophases of the samples were thermally and optically characterized by differential thermal analysis (DSC) and polarized optical microscopy (POM). All samples revealed enantiotropic smectic B (SmB) and smectic A (SmA) mesophases. The results obtained were further correlated with the density functional theory (DFT) theoretical calculations. The results are compared to a series of compounds bearing biphenyl moiety in their mesogens. The thermal stabilities of the different mesophase reduced upon the increment of the alkoxy chain length. The temperature ranges of both the smectic mesophases of new compounds bearing the 4-phenyl pyridine moiety are generally expanded higher than the other series. In addition, the total mesophase range is greater in the new compounds when compared to their biphenyl analogues. The DFT results were investigated in terms of the molecular geometries and the frontier molecular orbitals as well as the charge distribution mapping to show and illustrate the difference in the mesomorphic properties.

Supramolecular three-ring Schiff base novel liquid crystal complexes have been prepared and investigated. Schiff bases of para-substituted aniline derivatives and para-pyridine carbaldehyde have been prepared and then mixed in equimolar quantities with para-alkoxy benzoic acids. On one side, the alkoxy chain length varies from 8 to 16 carbon atoms. On the other side, terminal small compact groups substituting aniline with various polarities are used. Hydrogen-bonding interaction was elucidated by FTIR spectroscopy. The mesomorphic thermal and optical characteristics of the samples were obtained by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). All samples exhibit enantiotropic mesophases. Experimental results obtained for the induced mesophases were correlated with density functional theory (DFT) theoretical calculations. The results revealed that both the polar compact groups’ polarity and the alkoxy chain lengths contribute strongly to mesomorphic characteristics and thermal stabilities of the mesophases. Surprisingly, the observed values of enthalpy changes associated with the crystalline mesomorphic transitions lie in the range of 2.2–12.5 kJ/mol. However, the enthalpy changes corresponding to the mesomorphic–isotropic transitions vary from 0.9 to 13.9 kJ/mol, depending on the polarity of para-attached groups to the aniline moiety.

Supramolecular, low-melting (near or below 0.0 °C) ionic liquid crystals with two rings of Schiff bases were prepared and studied. The Schiff bases were synthesized using 4-substituted aniline derivatives and 4-pyridine carbaldehyde and then mixed in equimolar amounts with linear 1-bromoalkanes of different chain lengths, namely C6, C8, and C14. The mesomorphic behavior and thermal properties of the compounds were determined by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). Only the ionic liquids analogous with 1-bromotetradecane exhibit mesomorphic behavior. All, except the smectic A (SmA) monomorphic fluorine-substituted complex, show dimorphic enantiotropic mesophases, namely SmA followed by nematic (N) mesophases depending on the temperature rise. The DSC and POM results for the induced mesophases were then treated with density functional theory calculations (DFT). The results showed that both the polarity of the polar groups and the length of the alkyl groups strongly influence the mesomorphic properties of the ionic liquids.