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Seven new derivatives of 4-octyloxy-N-(4-substituted benzylidene) aniline have been synthesized. 4-Trifluoromethyl and 4-trifluoromethoxy derivatives exhibit stable smectic B and A phases, respectively, while both the 4-methyl and 4-methoxy derivatives have monotropic nematic phases. Fundamental liquid crystalline properties such as entropies of the phase transitions, microscopic textures, smectic layer spacings, orientational order parameters, and molecular dipole moments were determined. It has been revealed that moderately polar nature of these mesogens act to stabilizing monolayer smectic states. The smectic A phase of 4-trifluoromethoxy derivative exhibit very high orientational order. None of the disubstituted compounds, 3,5-bis(trifluoromethyl), 3,5-dimethyl, and 3,5-dimethoxy derivatives were mesogenic. The effect of terminal trifluoromethylation on the liquid crystalline properties is discussed.

The nature of the smectic Ad to nematic phase transition and the modes of molecular motion were investigated for the homologous mesogens, CBOOA, NBOOA, and their chain-deuteriated compounds. In NBOOA, the SA d[sbnd]N phase transition was found to be first order with a pronounced pretransitional decrease of the orientational order parameter, , both above and below the transition point, while in CBOOA the anomaly in was very small. Despite the different behaviours in terms of the orientational order, the dynamical aspects of molecular motion, probed by the-NMR relaxation, are quite similar. The motional mode characteristic of the N phase is order director fluctuation, but translational self-diffusion becomes the dominant relaxation mechanism in the SA d phase. It is also recognized that the relative importance of these mechanisms changes in a continuous manner as a function of temperature.

The nature of smectic A liquid crystals and the phase transitions from smectic A to nematic phases are studied in the homologous series of 4-(4″-octyloxy-benzoyloxy)benzylidene-4′-substituted anilines, in which the substituents are H, F, Cl, Br, I, NO2 and CN. Measurements have been performed for the dipole moment of the molecule, the smectic A lattice period, the temperatures and the entropies of phase transitions, and the temperature dependence of the orientational order parameter, all of which provide information on the intermolecular pair potentials. It is shown that the introduction of a terminal polar substituent brings about counteracting contributions to the stability of the smectic A state. It is suggested that the reentrant nematic phase transition can appear in the strongly polar mesogens if the extent of antiparallel association of the molecules increases on lowering the temperature.