Ferroelectric Liquid Crystals: Synthesis and Thermal Behavior of Optically Active, Three-Ring Schiff Bases and Salicylaldimines.

The chiral ferroelectric smectic C (SmC*) phase, characterized by a helical superstructure, has been well exploited in developing high-resolution microdisplays that have been effectively employed in the fabrication of a wide varieties of portable devices. Although, an overwhelming number of optically active (chiral) liquid crystals (LCs) exhibiting a SmC* phase have been designed and synthesized, the search for new systems continues so as to realize mesogens capable of meeting technical necessities and specifications for their end-use. In continuation of our research work in this direction, herein we report the design, synthesis, and thermal behavior of twenty new optically active, three-ring calamitic LCs belonging to four series. The first two series comprise five pairs of enantiomeric Schiff bases whereas the other two series are composed of five pairs of enantiomeric salicylaldimines. In each pair of optical isomers, the configuration of a chiral center in one stereoisomer is opposite to that of the analogous center in the other isomer as they are derived from (3 S)-3,7-dimethyloctyloxy and (3 R)-3,7-dimethyloctyloxy tails. To probe the structure-property correlations in each series, the length of the n-alkoxy tail situated at the other end of the mesogens has been varied from n-octyloxy to n-dodecyloxy. The measurement of optical activity of these chiral mesogens was carried out by recording their specific rotations. As expected, enantiomers rotate plane polarized light in the opposite direction but by the same magnitude. The thermal behavior of the compounds was established by using a combination of optical polarizing microscopy, differential scanning calorimetry, and powder X-ray diffraction. These complementary techniques demonstrate the existence of the expected, thermodynamically stable, chiral smectic C (SmC*) LC phase besides blue phase I/II (BPI or BPII) and chiral nematic (N*) phase. However, as noted in our previous analogous study, the vast majority of the Schiff bases show an additional metastable, unfamiliar smectic (SmX) phase just below the SmC* phase. Notably, the SmC* phase persists over the temperature range ≈80-115 °C. Two mesogens chosen each from Schiff bases and salicylaldimines were investigated for their electrical switching behavior. The study reveals the ferroelectric switching characteristics of the SmC* phase featuring the spontaneous polarization (PS ) in the range 69-96 nC cm-2 . The helical twist sense of the SmC* phase as well as the N* phase formed by a pair of enantiomeric Schiff bases and salicylaldimines has been established with the help of circular dichroism (CD) spectroscopic technique. As expected, the SmC* and the N* phase of a pair of enantiomers showed mirror image CD signals. Most importantly, the reversal of helical handedness from left to right and vice versa has been evidenced during the N* to SmC* phase transition, implying that the screw sense of the helical array of the N* phase and the SmC* phase of an enantiomer is opposite.

Fluorine containing nonsymmetrical five-ring achiral banana-shaped compounds with columnar and synclinic antiferroelectric layered phases.

The phase transitional behavior of two homologous series of five-ring banana-shaped compounds comprising fluorine substituents synthesized through covalent linking of two chemically dissimilar rod-like anisometric cores (arms) to central 1,3-phenylene is reported. The novelty of these molecules originates from the fact that the molecules are highly nonsymmetrical. One of the arms, which is either salicylaldimine or Schiff base core, possesses two vicinal fluorine atoms at the terminal ring having a -decyloxy tail; while the -alkyl tail attached to the other arm was varied to realize a homologous series of compounds. The mesophases have been characterized by several complementary studies. The banana-shaped systems having short or medium alkyl chain lengths form apolar columnar (two-dimensional) structures, while on ascending the series, a polar smectic phase is stabilized. Detailed electro-optical investigations on one of the polar smectic phases revealed a synclinic antiferroelectric (racemic) ground state structure, which switches, as expected, to an anticlinic ferroelectric state by the application of an electrical field. At higher field strengths applied for an extended time interval, the anticlinic ferroelectric state switches to a synclinic ferroelectric (chiral) state. Upon field removal, these domains switch to an anticlinic antiferroelectric (chiral) state, which eventually nucleates to the original antiferroelectric synclinic (racemic) state. Remarkably, the associated spontaneous polarization value exceeds 800 nC cm, which is among the highest reported hitherto.

Self-organization of mesomeric-ionic hybrid heterocycles into liquid crystal phases: a new class of polar mesogens.

The first mesoionic nematic and smectic A mesogens derived from sydnones that are characterized by both covalent and ionic features have been synthesized and evidenced by optical, calorimetric and X-ray diffraction studies.