Tuning the Liquid Crystallinity and Electroluminescence via Sulfonation of S-Annulated Perylene Tetraester.

This study presents a comparative analysis of S-annulated perylene tetraester (PTE-S) and its sulfone (PTE-SO2) analogue. This sulfone modification reduced melting point and stabilized a room temperature columnar rectangular (Colr) phase in contrast to its parent PTE-S which showed a crystalline behaviour at room temperature. This molecular design also leads to red-shifted absorbance and emission in comparison to PTE-S, along with a tuning of photoluminescence from sky blue to green, achieving an impressive quantum yield of 85 %. OLED devices fabricated using PTE-SO2 as emitter material at concentrations of 0.2, 0.5, and 1 wt.% in CBP as host material. A maximum external quantum efficiency (EQE) of 2.9 % was observed with the 0.5 wt.% PTE-SO2 in CBP with CIE coordinates of (0.45, 0.35), accompanied by an orange luminance of 848 cd/m2. Notably, a device with a 0.5 wt% doping concentration of PTE-S demonstrates an EQE of 3.5 %, and cyan luminance of 2,598 cd/m2.

Tris(boranil) Columnar Liquid Crystalline Fluorophores: pseudo-Triphenylene Boron(III) Complexes with Peripheral N-B-O Linkages.

The borate complexes derived from salicylaldimine ligands, called boranils, possess a wide range of photophysical and electronic characteristics intrinsically. The unique combination of molecular rigidity, rendered by four-coordinate boron bridges, and extended π-conjugation enable them to serve as technically feasible fluorescent materials (dyes). The incorporation of liquid crystallinity in these boron(III) complexes, especially the columnar (Col) mesomorphism, which is overlooked hitherto, would provide a new dimension to these complexes. Herein, we report the first examples of tris(boranil) discotic liquid crystal (LC) dyes that have been readily synthesized by treating tris(N-salicylideneaniline)s, (TSAN)s, with BF3 .Et2 O in the presence of an acid quencher. These C3 -symmetric borate complexes self-assemble into the Col phase, existing over a wide thermal span including room temperature. The 2D periodic order of the Col phases shows dependence on the length of the peripheral tails. The photophysical measurements reveal the fluorescence emission in their two condensed states viz., solid and Col phase, and in solution. Their electrochemical, two-step oxidation process coupled with the aforesaid features upholds their significance in applied research.

Topological defects due to twist-bend nematic drops mimicking colloidal particles in a nematic medium.

Colloids formed of solid/fluid particle dispersions in oriented nematic liquid crystals are known to be an ideal means of realizing fundamentally significant topological defect geometries. We find, experimentally, that twist-bend nematic (NTB) droplets formed in the N-NTB biphasic regime, either of pure compounds or mesogenic mixtures, completely mimic colloidal particles in their ability to generate a rich variety of defects. In the biphasic regime, the topological features of both liquid crystal colloids and chiral nematic droplets are revealed by (i) topological dipoles, quadrupoles and their patterned clusters formed in planar nematic liquid crystals orientationally perturbed by coexisting NTB drops, (ii) the transformation of hyperbolic hedgehogs into knotted Saturn rings encircling the NTB drops dispersed in a 90°-twisted nematic matrix and (iii) the Frank-Pryce defect texture evident in smaller (relative to sample thickness) NTB drops. In larger drops with fingerlike outgrowths, additional line defects appear; most of these are deemed to be pairs of disclinations to which are attached pairs of screw dislocations intervening in the growth process of the NTB droplets.

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.

Instabilities in the electric Freedericksz state of the twist-bend nematic liquid crystal CB7CB.

We report on the instabilities in the Freedericksz state of the twist-bend nematic (NTB) liquid crystal 1'',7''-bis(4-cyanobiphenyl-4'-yl)heptane (CB7CB). The quasi homeotropic NTB state, into which a planar (untwisted or 90°-twisted) nematic CB7CB layer transits under a strong electric field, is found to be unstable despite the material being dielectrically positive. Close to the NTB melting point, destabilization occurs through the formation of metastable toric focal conic domains (TFCDs) that, in time, transform into parabolic focal conic domains (PFCDs) with the confocal parabolae in vertical planes through the layer normal. This transformation occurs by a novel process of continued dissociation of TFCDs. We outline how the extended Volterra process could help in a general appreciation of focal conic defects in the NTB phase. At relatively lower temperatures, stripes develop competingly with TFCDs. Identifiable as oily streaks, they are both localized and polarity sensitive; they form close to the substrates; and in low frequency square wave fields, they get suppressed at the cathode and augmented at the anode at each polarity switch. The study also dwells on the N-NTB-N sandwich region, found between the N and NTB states under a small temperature gradient.

Interfacial and morphological features of a twist-bend nematic drop.

In this experimental and theoretical study, we examine the equilibrium shapes of quasi-two-dimensional twist-bend nematic (Ntb) drops formed within a planarly aligned nematic layer of the liquid crystal CB7CB. Initially, at the setting point of the Ntb phase, the drops assume a nonequilibrium cusped elliptical geometry with the major axis orthogonal to the director of the surrounding nematic fluid; this growth is governed principally by anisotropic heat diffusion. The drops attain equilibrium through thermally driven dynamical evolution close to their melting temperature. They are associated with a characteristic twin-striped morphology that transforms into the familiar focal conic texture as the temperature is lowered. At equilibrium, large millimetric drops are tactoidlike, elongated along the director of the surrounding nematic fluid. This geometry is explained using a mathematical model that features two dimensionless parameters, of which one is the structural cone angle of the Ntb phase and the other is the relative strength of mismatch elastic energy at the drop's interface. Both parameters are extracted from the observations by measuring the aspect ratio of the equilibrium shapes and the inner corner angle of the cusps.

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.

Phase behaviour and adsorption of deoxyribonucleic acid onto an azobenzene liquid crystalline ligand at the interfaces.

Azobenzene liquid crystalline (ALC) ligand contains a cholesteryl group linked to an azobenzene moiety through a carbonyl dioxy spacer (C7) and terminated with an amine group as a polar head. The phase behaviour of the C7 ALC ligand at the air-water (A-W) interface is investigated employing surface manometry. The surface pressure-area per molecule isotherm shows that C7 ALC ligand exhibit two different phases following the phase sequence viz., liquid expanded (LE1 and LE2) and then collapse to three-dimensional crystallites. Further, our investigations under different pH conditions and in the presence of DNA reveal the following. Compared to the bulk, the acid dissociation constant (pKa) of an individual amine reduces to 5 at the interfaces. For pH (3.5) < pKa, the protonation of amine groups of C7 ALC ligand facilitates the condensation of the film and enhances the stability. For pH values > pKa, the phase behaviour of the ligand remains the same due to the partial dissociation of the amine groups. The presence of DNA in the sub-phase result in the expansion of isotherm to the higher area per molecule and the compressional modulus extracted reveals the phase sequence; liquid expanded, liquid condensed, followed by a collapse. Further, the kinetics of adsorption of DNA to the amine groups of the ligand is investigated, suggesting the interactions are influenced by surface pressure corresponding to different phases and pH of the sub-phase. Brewster angle microscope studies are carried out at different surface densities of the ligand as well as in the presence of DNA also supports this inference. Atomic force microscope is employed to acquire the surface topography and height profile of C7 ALC ligand (1 layer) after transferring on onto a silicon substrate using Langmuir Blodgett deposition. The difference in the surface topography and thickness of the film indicates the adsorption of DNA onto the amine groups of the ligand. The characteristic UV-visible absorption bands of the ligand films (10 layers) at the air-solid interface are tracked and the hypsochromic shift of these bands is also attributed to these DNA interactions.

Twist-bend nematic drops as colloidal particles: Electric instabilities.

The mesogen 1,''7''-bis(4-cyanobiphenyl-4'-yl)heptane (CB7CB), doped with a small quantity of an amphiphilic compound, is examined in its biphasic state in which twist-bend nematic (N_{TB}) drops are dispersed in the isotropic fluid. Various flexoelectric and electrokinetic responses of small drops in their escaped-radial-like (ER) geometry, and also of larger ones with parabolic focal conic defects, are discussed. A pair of confocal parabolas with their axes along the applied low-frequency electric field undergo periodic dimensional changes so as to contribute flexoelectrically to free-energy reduction. In an ER droplet, the same result is achieved by periodic relocations of the hedgehog core. Sine-wave fields of low frequency and high voltage excite patterned states near zero-voltage crossings and homeotropic alignment at peak voltages. ER drops also exhibit electrohydrodynamic effects; in relatively weak fields, they undergo translatory motion with a velocity that is a quadratic in the field strength; the drift, which occurs over a very wide frequency range, extending from dc to MHz region, is enabled by radial symmetry breaking that their off-centered geometry entails; and the drift direction reverses across a critical frequency. In high fields, vortical flows occurring within an ER N_{TB} drop become discernible. The hydrodynamic effects are discussed based on the Taylor-Melcher leaky dielectric model.

Twist-bend nematic drops as colloidal particles: Structural features.

The mesogen CB7CB [1″,7″-bis(4-cyanobiphenyl-4'-yl)heptane], mixed with a small quantity of a long chain amphiphile, is examined for the structural features of twist-bend nematic (N_{TB}) drops acting as colloidal inclusions in the isotropic and nematic environments. In the isotropic phase, the drops nucleating in the radial (splay) geometry develop toward escaped radial, off-centered structures, involving both splay and bend distortions. With further growth, they transform into low-birefringence (near-homeotropic) objects, within which remarkably well-organized networks of parabolic focal conic defects evolve in time. In electrically reoriented near-homeotropic N_{TB} drops, the pseudolayers develop an undulatory boundary possibly attributable to saddle-splay elasticity. In the matrix of the planar nematic phase, N_{TB} droplets appearing as radial hedgehogs attain stability in the dipolar geometry, through their association with hyperbolic hedgehogs. With growth, on transformation of the hyperbolic defect into its topologically equivalent Saturn ring around the N_{TB} drop, the geometry turns quadrupolar. Significantly, dipoles are stable in smaller drops, while quadrupoles are stable in larger ones. The dipole-quadrupole transformation is reversible, but is hysteretic with respect to drop size. Importantly, this transformation is often mediated by nucleation of two loop disclinations, one appearing at a marginally lower temperature than the other. The existence of a metastable state with partial formation of a Saturn ring and persistence of the hyperbolic hedgehog raises a question relating to the conservation of topological charge. In twisted nematics, this state features in the formation of a giant unknot that binds all N_{TB} drops together.

Laterally substituted symmetric and nonsymmetric salicylideneimine-based bent-core mesogens.

Bent-core mesogens have gained considerable importance due to their ability to form new mesophases with unusual properties. Relationships between the chemical structure of bent-core molecules and the type and physical properties of the formed mesophases are relatively unknown in detail and differ strongly from those known for calamitic liquid crystals. In this paper symmetric and nonsymmetric five-ring salicylideneaniline-based bent-core mesogens are presented, and the effect of lateral substituents attached at the outer phenyl rings (F, Cl, Br) or the central phenyl ring (CH(3)) on the liquid-crystalline behaviour and on the physical properties is studied. Corresponding benzylideneaniline-based compounds were additionally prepared in order to study the influence of the intramolecular hydrogen bond. The occurring mesophases were investigated by differential scanning calorimetry, polarising microscopy, X-ray diffraction and dielectric and electro-optical measurements. The paper reports on new findings with respect to the structure-property relationships of bent-core mesogens. On one hand, the disruptive effect of laterally substituted halogen atoms, F, Cl and Br, on the mesophase behaviour of three isomeric series was much lower than expected. On the other hand, an increase of the clearing temperature by 34 K was observed, caused by small lateral substituents. The electro-optical behaviour, especially the type of polar switching and corresponding molecular movements, is sensitive to variations in the molecular structure.

Structure, stability, and electro-optic features of nematic drops in 1

Binary mixtures of the mesogen [1″,7″-bis(4-cyanobiphenyl-4'-yl)heptane] and a long chain amphiphile (e.g., 2-octadecoxypropanol) are examined for the structure, stability, and electro-optical behavior of nematic drops dispersed in the isotropic phase, in planar cells. Subjected to tangential boundary conditions, the drops adopt, besides the escaped concentric and untwisted bipolar geometries, the less common bound vortex geometry with a pair of half-strength disclination lines. The concentric drop, as it grows, switches its axis from an in-layer to the layer-normal direction corresponding to the stablest of all geometries. Bipolar drops in equilibrium have their axes parallel to the easy axis of the cell. Obliquely oriented bipolar drops rotate to attain the equilibrium disposition by the shorter of the clockwise and anticlockwise routes, the extent of rotation decreasing exponentially with time. The bipolar structure is marginally less stable than the concentric, and transforms to the latter geometry occasionally. In bound vortex drops, the separation between the lines varies as the drop diameter, the bipolar and concentric geometries appearing as the limiting cases. The complex course of Fréedericksz transition in all the different types of drops terminates in the division of the original large drop into many smaller drops, each with a surface charge 2, in conformity with the Poincaré-Hopf theorem. In low frequency electric fields, concentric drops exhibit flexoelectro-optic rotation in evidence of their escaped character.

Exceptionally Wide Thermal Range Enantiotropic Existence of a Highly Complex Twist Grain Boundary Phase in a Pure, Single-Component Liquid Crystal Chiral Dimer.

Twist grain boundary (TGB) phases exhibiting highly frustrated and complex liquid crystal structures have aroused enormous interest because of their close resemblance to superconductors. The remarkable experimental demonstration of their occurrence by Goodby and co-workers paved the way for developing new research endeavors. However, of the several genuine concerns associated with these intriguing structures, their temperature range has been challenging. In this communication, we report the occurrence of the TGB phase with smectic C* blocks (TGBC*) over a vast, unprecedented thermal range of ∼170 °C in a newly synthesized chiral dimer derived from cholesterol. Detailed investigations covering synthesis, characterization, and evaluation of liquid crystallinity with the aid of optical, calorimetric, and X-ray diffraction are presented.

Chiral plasmonic liquid crystal gold nanoparticles: self-assembly into a circular dichroism responsive helical lamellar superstructure.

Owing to their proven and promising potential in various technological endeavors ranging from catalysis and sensing to invisibility cloaks made from metamaterials, chiral plasmonic superstructures resulting from the directed self-assembly of optically active metal nanoparticles (MNPs) have been pursued intensively in recent years. Several strategic efforts have emerged especially to accomplish advanced nanomaterials assembling into liquid crystalline (LC) helical structures, where MNPs are regularly packed in fluid/frozen arrays/layers or wires (columns). While the helical fluid columnar arrays (molecular wires) showing circular dichroism (CD) have been realized, the discovery of fluid chiral lamellar ordering, where the dielectric and conducting regimes are arranged alternatively, has hitherto remained highly elusive. Herein we report the first examples of monodisperse LC-gold NPs (LC-GNPs) self-assembling into a fluid/frozen lamellar structure exhibiting CD activity. Notably, these new, exceptional LC-GNPs have been realized by simple, hassle-free protocols that involve the room temperature addition of LC dimer-like arylamines to Au(iii), where the amines not only reduce Au(iii) to Au(0) but also bind strongly to the central GNP scaffold. Their molecular structure, mesomorphism, and ability to interact with circularly polarized light have been evidenced unambiguously and could play an important role in realizing metamaterials in the visible region.

Photo-tunable epsilon-near-zero behavior in a self-assembled liquid crystal - nanoparticle hybrid material.

Dynamic tuning of electromagnetic response is an important parameter to realize exotic applications of optical metamaterials. Self-assembly achieved via the incorporation of soft materials is an attractive approach to achieve tunable optical properties. Among the soft materials, liquid crystals are highly sought after due to the inherent soft-stimuli responsiveness. This article reports experimental evidence of tunable epsilon-near-zero (ENZ) behavior brought about by an optical field in a self-assembled liquid crystal - nanoparticle system. The material consists of Au nanoparticles capped with a photo-active chiral liquid crystal ligand. In the liquid crystalline state, the system self-assembles into a helical lamellar superstructure, confirmed by polarizing optical microscopy, HRTEM, XRD, and circular dichroism studies. Upon irradiation with UV light, the localized surface plasmon resonance peak of Au red-shifts by ∼10 nm and gets restored with white light illumination. The effective permittivity of the system obtained from ellipsometry indicates ENZ behavior in the visible spectrum with a bandwidth of ∼45 nm which gets enhanced by a factor of 1.6 on UV illumination. Theoretical calculations, carried out using the effective medium approach, support the experimental findings, making the system an efficient ENZ metamaterial in the optical regime.

Electric response of topological dipoles in nematic colloids with twist-bend nematic droplets as the dispersed phase.

Colloidal systems comprising solid or fluid particles dispersed in nematic monodomains are known to be a convenient means to study topological defects. Recent experiments have shown that twist-bend nematic (N_{TB}) droplets in a nematic matrix act as colloidal particles that lead to the formation of elastic dipoles, quadrupoles, and their ordered clusters. In this study, we examine the effect of low-frequency (f∼mHz) electric fields on such defect configurations. We find that (i) the hyperbolic hedgehogs of elastic dipoles shift toward the negative electrode in static fields and perform oscillatory motion in AC fields, indicating the presence of nonvanishing flexoelectric polarization in the field-free state; (ii) the elastic dipoles, propelled by forces of backflow due to coupled flexoelectric and dielectric distortions, drift uniformly along their axes with the N_{TB} drops in lead; (iii) the translational velocity v_{d} increases linearly with both f and the diameter of N_{TB} drops; and (iv) with increasing applied voltage U, v_{d}(U) exhibits a monotonic, slightly nonlinear variation at f≤200mHz, tending toward linearity at higher frequencies.

Room-Temperature, Deep-Red/NIR-Emissive, C 3-Symmetric (n,π-conjugated) Columnar Liquid Crystals: C 3h -Tris(keto-hydrazone)s.

The first examples of deep-red/near-infrared (NIR) photoluminescent, (n,π-conjugated) discotics, namely, C 3h -tris(keto-hydrazone)s, which are the tautomers of tris(azo-enol)s, have been synthesized via a facile one-step triple azo-coupling and characterized. The n,π-resonance-assisted intramolecular H-bonding, rendering planarity and shape persistence to the central core, facilitates their self-assembly into either a hexagonal columnar (Colh) phase (p6mm lattice) or a columnar rectangular (Colr) phase (p2mm lattice), over an extended thermal range including room temperature, fluorescing in the deep-red/NIR-I region. The low band gap with deep-red/NIR emission makes them ideal candidates for NIR-organic light-emitting diodes (OLEDs) and bioimaging.

Effect of Photonic Band Gap on Photoluminescence in a Dye-Doped Blue Phase Liquid Crystal.

Tunability of fluorescence intensity is an essential parameter for enhancing the versatility of devices like emissive displays and solar cells. Soft photonic crystals, with their tunable photonic band gap (PBG), are highly sought-after systems for such purposes. Here, we report modulation of photoluminescence (PL) intensity in a fluorescent dye-doped blue phase liquid crystal, a 3D soft photonic crystal. On cooling, from the isotropic fluid phase, the PL intensity gets enhanced due to the overlapping of the emission wavelength of the dye with the photonic band edge. However, the PL intensity decreases on the application of an electric field, despite both thermal and electric fields having a similar effect (red shift) on the PBG. The contrasting behavior of PL intensity, also observed in composites obtained by varying the dye and the chiral dopant (handedness), is discussed in terms of scattering pathways for the emitted photons. The time-resolved PL studies show a reduction in the lifetime of the excited species upon cooling, validating the thermal dependence of PL intensity modulation due to Purcell effect. The facile modulation of PL intensity in the dye-doped blue phase system makes it appealing from the point of view of high-performance photonic applications.

Saddle-splay-induced periodic edge undulations in smectic-A disks immersed in a nematic medium.

We report experimental studies on the phase behavior of binary mixtures of 1″,7″-bis(4-cyanobiphenyl-4'-yl)heptane (CB7CB) and 4,4-diheptyloxyazoxybenzene, which exhibit, apart from the nematic (N) and twist-bend nematic (N_{TB}) phases, the induced smectic-A (Sm-A) phase for weight fraction of CB7CB between 0.05 and 0.70. In planar nematic layers, the N_{TB} phase separates as droplets of tactoidlike planform; the chirality of droplets manifests in the optical dissimilarity between their opposite angular ends. Our main result is that, in the appropriate two phase region, Sm-A nuclei with positive dielectric anisotropy change over to disks immersed in the nematic above some electric field, their edges decorated by periodic bright spots, a result which was earlier reported in another binary system exhibiting the induced Sm-A phase [R. Pratibha and N. V. Madhusudana, Physica A 224, 9 (1996)10.1016/0378-4371(95)00311-8]. We develop a simple theory for the threshold of this distortion, which is a periodic undulation of the edge of the disk, demonstrating that it arises from saddle-splay elasticity of Sm-A, the low Sm-A-N interfacial tension unable to suppress the distortion. The observed increases in the number of bright spots with field, and with the radius of the disk at a given field, in both the experimental systems are also accounted for by the model. The distortion, which results in the most direct visualization of saddle splay in Sm-A, is also exhibited by disks nucleating on surfaces treated for homeotropic anchoring.

Luminescent, liquid crystalline tris(N-salicylideneaniline)s: synthesis and characterization.

A new class of discotics derived from tris(N-salicylideneaniline)s have been synthesized and their thermal and photophysical properties are investigated. These systems with outer 1,3,4-oxadiazole wings exist in an inseparable mixture of two keto-enamine tautomeric forms with C(3h) and C(s) rotational symmetries, and self-assemble into fluid columnar phase over a wide thermal range as evidenced by several complementary studies. They possess emissive characteristics in both solution and columnar states; the blue light (lambda = 474 nm) emission has been evidenced for the former state.