Light-Emitting Chiral Nematic Dimers with Anomalous Odd-Even Effect.

In this report, based on the results derived from the extensive study into the thermal and photophysical properties, an anomalous mesomorphic behavior of photoluminescent, chiral nematic (N*) liquid crystalline dimers, belonging to two different series has been revealed. They comprise cholesterol and fluorescent three-ring Schiff base or salicylaldimine core interlinked via an ω-oxyalkanoyloxy spacer of varying length and parity. The effect of molecular structure on the liquid crystal (LC) behavior and photophysical properties of both the series has been probed by varying the length of the terminal n-alkoxy tails for a fixed (odd or even) parity of the spacer. The detailed investigations using complementary techniques not only evidenced the existence of the N* phase in all the dimers synthesized but also the occurrence of an intriguing odd-even effect; blue phases (BPs) exist in all the dimers comprising even-membered spacer, which surprisingly remains totally absent in their odd-membered counterparts. While the results reported hitherto are exactly opposite to the aforesaid findings, this atypical behavior has been interpreted in terms of the over-all shape of the dimers rendered by the orientation of terminal tails. Photophysical studies carried out clearly revealed the intrinsic light emitting feature of the dimers not only in their dilute solutions but also in their three condensed states viz., solid, N* phase, and isotropic liquid state; the emission intensities of the N* phase varies with the change in temperature, as expected. CD spectra of the N* phase recorded as a function of temperature show bisignate CD band characteristically, signifying large chiral correlations in the molecular self-assembly, while the origin of bands from positive to negative region suggests a right-handed twist of the N* helix.

Dynamic Orthogonal Switching of a Thermoresponsive Self-Organized Helical Superstructure.

Controllable manipulation of self-organized dynamic superstructures of functional molecular materials by external stimuli is an enabling enterprise. Herein, we have developed a thermally driven, self-organized helical superstructure, i.e., thermoresponsive cholesteric liquid crystal (CLC), by integrating a judiciously chosen thermoresponsive chiral molecular switch into an achiral liquid crystalline medium. The CLC in lying state, in both planar and twisted nematic cells, exhibits reversible in-plane orthogonal switching of its helical axis in response to the combined effect of temperature and electric field. Consequently, the direction of the cholesteric grating has been observed to undergo 90° switching in a single cell, enabling non-mechanical beam steering along two orthogonal directions. The ability to reversibly switch the cholesteric gartings along perpendicular directions by appropriately adjusting temperature and electric field strength could facilitate their applications in 2D beam steering, spectrum scanning, optoelectronics and beyond.

Influence of virtual surfaces on Frank elastic constants in a polymer-stabilized bent-core nematic liquid crystal.

Effect of a polymer network on the threshold voltage of the Fréedericksz transition, Frank elastic constants, switching speed, and the rotational viscosity are investigated in a polymer-stabilized bent-core nematic liquid crystal with different polymer concentrations. These polymer networks form virtual surfaces with a finite anchoring energy. The studies bring out several differences in comparison to similar studies with a calamitic liquid crystal as the nematic host. For example, on varying the polymer content the threshold voltage decreases initially, but exhibits a drastic increase above a critical concentration. A similar feature-reaching a minimum before rising-is seen for the bend elastic constant, which gets enhanced by an order of magnitude for a polymer content of 2.5 wt %. In contrast, the splay elastic constant has a monotonic variation although the overall enhancement is comparable to that of the bend elastic constant. The behavior changing at a critical concentration is also seen for the switching time and the associated rotational viscosity. The presence of the polymer also induces a shape change in the thermal dependence of the bend elastic constant. We explain the features observed here on the basis of images obtained from the optical and atomic force microscopy.

Diminished Splay Stiffening in Weak Gels of Calamitic-Bent-Core Nematic Composites.

Composites of calamitic and bent-core nematic molecules exhibiting a nematic to nematic-gel transformation have been investigated using thermal, electrical, X-ray, and mechanical probes. The studies focusing on the Frank elastic behavior show a surprising result that the thermal behavior of the threshold voltage and the dependent splay elastic constant (K11) are remarkably different in temperature regions identified as weak and strong gels. In the former gel, the parameters exhibit values significantly smaller than the higher-temperature fluid nematic, effectively canceling out the underlying thermal variation due to the order parameter. This is especially attractive from the viewpoint of display devices. The X-ray diffraction data suggest that the fibers have a plastic nature in the weak gel and 3D-crystalline ordering in the strong gel. We argue that the different elastic behavior in the two gel phases is caused by the nature of the fibers; they are stiff in both gels but the interfiber interaction is weaker in the weak gel allowing the splay elastic constant to be lowered. The X-ray and rheological data lend support to the characterization of the fibers.

Influence of polarization-tilt coupling on the ferroelectric properties of smectic gels.

We have studied composites of a ferroelectric liquid crystal mixture with a simple organic gelating agent, employing structural, thermal, electrical and mechanical probes, investigating the influence of the coupling between the polarization and the tilt angle on the ferroelectric properties of smectic gels. The calorimetric data, presenting clear signatures of the gelation occurring in the smectic A (SmA) phase or the isotropic phase, depending on the concentration of the gelator, help in constructing a rich diagram in the temperature-gelator concentration phase space. The atomic force microscopy imaging brings out the interesting feature of the transfer of chirality from the ferroelectric liquid crystal (FLC) to the gel strands, as exemplified by the creation of nanorope structures which have attracted much attention in recent times. The influence of gelation on the magnitude of the tilt angle appears to be dependent on the probe employed: there is no change in the values obtained by X-ray diffraction, which looks at the projection of the entire molecular length onto the layer normal. In contrast, the value from the electro-optic method, wherein the molecular-core is responsible for the results, diminishes with gelator concentration. The latter feature is copied by the magnitude of the polarization also. Dielectric spectroscopy shows that gelation weakly influences the soft mode in the SmA phase. However, the Goldstone mode behaviour is strongly dependent on the gelator concentration, with the appearance of two modes in the smectic C* (SmC*) phase of higher gel concentrations. With information obtained upon application of DC bias, the origin of the two relaxations is discussed. These data are analyzed in terms of the predictions of the Landau model proposed for the ordinary (non-gel) SmA-SmC* transition showing that the gel network enhances the linear polarization-tilt coupling over the biquadratic one. Upon gelation the system becomes mechanically strong with a large increase in the elastic moduli.

Self-assembly of hekates-tris(N-salicylideneaniline)s into columnar structures: synthesis and characterization.

Two series of new, photoluminescent star-shaped discotic liquid crystals, recently termed as "hekates", derived from tris(N-salicylideneaniline)s (TSANs), were synthesized by the facile threefold condensation of 3,4-bis(alkoxy)phenyl 4-aminobenzoates/3,4,5-tris(alkoxy) phenyl 4-aminobenzoates with 1,3,5-triformylphloroglucinol and characterized. These two series of discotics with six and nine peripheral n-alkoxy tails were especially designed and accomplished to understand the relation between mesomorphic/photophysical properties and molecular structure. Proton NMR spectral analysis revealed their existence as an inseparable mixture of two keto-enamine tautomeric forms featuring C(3h) and C(s) rotational symmetries. A systematic study into the thermotropic liquid crystal behavior using polarizing optical microscopy, differential scanning calorimetry, and X-ray scattering confirmed the presence of columnar (Col) phase in vast majority of the TSANs prepared. The two-dimensional (2D) lattices of these fluid columnar phases were found to be characteristic of hexagonal Col (Col(h)), rectangular Col (Col(r)), or oblique Col (Col(ob)) phases depending on the number/length of the peripheral flexible chains. The stabilization of the Col(ob) phase, a less commonly found fluid columnar structure, and the first of its kind in TSAN systems, implies very intensive intermolecular (face-to-face) interactions among the TSAN cores within the column. The photophysical properties were investigated both in solution and the columnar states by UV-vis absorption and photoluminescence; markedly, the solution state emits light in the blue region. The light-emitting ability of the Col phase is particularly significant given the possibility that, in such cores, the protons and electrons interact with each other through the H-bonding environment.

Permittivity, conductivity, elasticity, and viscosity measurements in the nematic phase of a bent-core liquid crystal.

We report on measurements of dielectric permittivity epsilon, electrical conductivity sigma, elastic moduli k(ii), and rotational viscosity gamma for a bent-core nematic liquid crystal. The static permittivity anisotropy epsilon(a) = epsilon(parallel)-epsilon(perpendicular) is negative; at a given temperature in the interval 107-123 degrees C, epsilon(parallel) shows two relaxations falling in the frequency bands 20-200 kHz and 0.9-2 MHz; epsilon(perpendicular) also shows a relaxation between 0.9 and 5 MHz. The conductivity anisotropy sigma(a) = sigma(parallel)-sigma(perpendicular) is negative at low frequencies; it changes sign twice at frequencies f(1) and f(2) that increase with temperature, in the ranges 6.5-10 and 95-600 kHz, respectively. Surprisingly, the splay modulus k(11) is considerably greater than the bend modulus k(33) in the entire nematic range. Viscous relaxation is more complex than in calamitic systems involving at least a two-step process. The gamma values are an order of magnitude greater compared to calamitics.

Patterned electroconvective states in a bent-core nematic liquid crystal.

We report the results of investigations on the anisotropic electrohydrodynamic states arising in a highly conducting, planarly aligned, bent-core nematic liquid crystal driven by ac fields of frequency f in the range from 10 Hz to 1 MHz. Pattern morphologywise, two f regimes are distinguished. The low-f regime, wherein the primary bifurcation is to a state of periodic longitudinal stripes (LS), extends to an unprecedentedly large f, in the range 150-550 kHz, depending on the temperature T. This is followed by the high-f regime wherein periodic normal stripes (NS) constitute the primary instability. Both instabilities involve predominant director modulations and streamlines in the layer plane. The transitional frequency between the two regimes is linear in temperature. The curve V(c)(f) shows a nonlinear increase for the LS state and decrease for the NS state. V(c)(T) is an ever increasing curve close to the nematic-isotropic point for both states. The wavenumber of LS varies directly as V, and that of NS shows nearly the same behavior. The pattern period versus f is increasing for LS but decreasing for NS. Both instability states exhibit complex, light-polarization-dependent lens action. Well above the threshold, disclination loops of regular geometry appear along the stripes. They drift in a coordinated manner along the flow lines. At very high voltages, the instability turns strongly time dependent. The current models of anisotropic convection based on static electrical parameters fail to account for the observed instabilities.

Converse flexoelectric effect in bent-core nematic liquid crystals.

We report on the converse flexoelectric effect in two bent-core nematic liquid crystals with opposite dielectric anisotropies. The results are based on electro-optic investigations of inplane field-driven distortions in homeotropic samples (the Helfrich method). They are interpreted by an extension of the Helfrich theory that takes into account the higher order distortions. The bend flexocoefficient for both the compounds is of the usual order of magnitude as in calamitics, unlike in a previously investigated bent-core nematic for which giant values of the bend flexocoefficient are reported. In order to resolve this discrepancy, we propose a molecular model with nonpolar clusters showing quadrupolar flexoelectricity. The study also includes measurements on surface polarization instabilities in the dielectrically positive material; the splay flexocoefficient thereby deduced is also of the conventional order.

Electroconvection in a homeotropic bent-rod nematic liquid crystal beyond the dielectric inversion frequency.

We characterize the structural transitions in an initially homeotropic bent-rod nematic liquid crystal excited by ac fields of frequency f well above the dielectric inversion point fi. From the measured principal dielectric constants and electrical conductivities of the compound, the Carr-Helfrich conduction regime is anticipated to extend into the sub-megahertz region. Periodic patterned states occur through secondary bifurcations from the Freedericksz distorted state. An anchoring transition between the bend Freedericksz (BF) and degenerate planar (DP) states is detected. The BF state is metastable well above the Freedericksz threshold and gives way to the DP state, which persists in the field-off condition for several hours. Numerous +1 and -1 umbilics form at the onset of BF distortion, the former being largely of the chiral type. They survive in the DP configuration as linear defects, nonsingular in the core. In the BF regime, not far from fi, periodic Williams-like domains form around the umbilics; they drift along the director easy axis right from their onset. With increasing f, the wave vector of the periodic domains switches from parallel to normal disposition with respect to the c vector. Well above fi, a broadband instability is found.

Drifting periodic structures in a degenerate-planar bent-rod nematic liquid crystal beyond the dielectric inversion frequency.

We report on the electric-field-generated effects in the nematic phase of a twin mesogen formed of bent-core and calamitic units, aligned homeotropically in the initial ground state and examined beyond the dielectric inversion point. The bend-Freedericksz (BF) state occurring at the primary bifurcation and containing a network of umbilics is metastable; we focus here on the degenerate planar (DP) configuration that establishes itself at the expense of the BF state in the course of an anchoring transition. In the DP regime, normal rolls, broad domains, and chevrons (both defect-mediated and defect-free types) form at various linear defect-sites, in different regions of the frequency-voltage plane. A significant novel aspect common to all these patterned states is the sustained propagative instability, which does not seem explicable on the basis of known driving mechanisms.

Instabilities across the isotropic conductivity point in a nematic phenyl benzoate under AC driving.

We characterize the sequence of bifurcations generated by ac fields in a nematic layer held between unidirectionally rubbed ITO electrodes. The material, which possesses a negative dielectric anisotropy epsilona and an inversion temperature for electrical conductivity anisotropy sigmaa, exhibits a monostable tilted alignment near TIN, the isotropic-nematic point. On cooling, an anchoring transition to the homeotropic configuration occurs close to the underlying smectic phase. The field experiments are performed for (i) negative sigmaa and homeotropic alignment, and (ii) weakly positive sigmaa and nearly homeotropic alignment. Under ac driving, the Freedericksz transition is followed by bifurcation into various patterned states. Among them are the striped states that seem to belong to the dielectric regime and localized hybrid instabilities. Very significantly, the patterned instabilities are not excited by dc fields, indicating their possible gradient flexoelectric origin. The Carr-Helfrich mechanism-based theories that take account of flexoelectric terms can explain the observed electroconvective effects only in part.

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.