Bent-core Liquid Crystal Molecules Research Articles

Control of the Induced Handedness of Helical Nanofilaments Employing Cholesteric Liquid Crystal Fields.

In this paper, a simple and powerful method to control the induced handedness of helical nanofilaments (HNFs) is presented. The nanofilaments are formed by achiral bent-core liquid crystal molecules employing a cholesteric liquid crystal field obtained by doping a rod-like nematogen with a chiral dopant. Homochiral helical nanofilaments are formed in the nanophase-separated helical nanofilament/cholesteric phase from a mixture with a cholesteric phase. This cholesteric phase forms at a temperature higher than the temperature at which the helical nanofilament in a bent-core molecule appears. Under such conditions, the cholesteric liquid crystal field acts as a driving force in the nucleation of HNFs, realizing a perfectly homochiral domain consisting of identical helical nanofilament handedness.

Directing the Handedness of Helical Nanofilaments Confined in Nanochannels Using Axially Chiral Binaphthyl Dopants.

In this work, we demonstrate control of the handedness of semicrystalline modulated helical nanofilaments (HNFmods) formed by achiral bent-core liquid crystal molecules by axially chiral binaphthyl-based additives as guest molecules solely under spatial nanoconfinement in anodic aluminum oxide nanochannels. The molecules of the same chiral additives are expelled from the HNFmods in the bulk, and as a result thereof do not affect the handedness or helical pitch of bulk HNFmods, resulting in an HNFmod conglomerate with chirality-preserving growth within each domain. However, under confinement these axially chiral guest molecules, likely embedded in the HNFmod host, do affect the helicity of the HNFmods. The configuration of the axially chiral molecules decides the HNFmod helix handedness and their concentration, and the helix angle is related to the helical pitch of the HNFmods. In addition to local imaging data obtained by scanning electron microscopy, global studies by thin-film circular dichroism spectropolarimetry support the imaging results.

Tuning the fluorescence behavior of liquid crystal molecules containing Schiff-base: Effect of solvent polarity

We report the influence of intermolecular and intramolecular hydrogen bonding on the excited state proton transfer (ESPT) emission behavior of two bent core liquid crystal (BLC) molecules, C 54 H 63 NO 9 (BLC3) and C 60 H 75 NO 9 (BLC4), having a Schiff-base and two long alkyl chains at its two ends. Fluorescence spectra of these BLC molecules dispersed in different solvents show dual emission (at � 365 nm and �425 nm) from the keto and enol tautomers. We observed that the population of these keto and enol tautomers and the corresponding intensities of fluorescence emission are strongly influenced by the solvent polarity. In protic solvents, formation of intermolecular hydrogen bond with the Schiff-base of the BLC molecules is highly favoured than the intramolecular hydrogen bonding. This intermolecular hydrogen bonding drastically reduces the population of the keto tautomers in the excited state, resulting in enhanced enol fluoroscence band along with a weak keto emission band. The observed intensity of the enol fluorescence band is the highest for the most studied polar solvent (methanol). On the other hand, in aprotic solvents, the intramolecular hydrogen bonding is highly favoured, which leads to the formation of keto tautomers in the excited state. Hence, an intense keto emission band is observed for the aprotic solvents along with a weak enol emission band. From the time resolved fluorescence studies we observed a longer life time for the keto band than that for the enol band. This is also related to the delayed emission associated with the vibrational bands resulting from the bulky alkyl chains attached to the ends of the BLC molecules. © 2019 Elsevier B.V.

Effect of Conformational Chirality on Optical Activity Observed in a Smectic of Achiral, Bent-Core Molecules.

Smectics of achiral, tilted bent-core liquid crystal molecules are chiral, but their optical activity is generally small. Here, we study the effect of conformational chirality on optical activity in smectic phases of an achiral, bent-core mesogen, W513. The neat material has a modulated B4 phase, which appears dark under crossed polarizers and shows no observable optical rotation under decrossed polarizers. However, mixtures of W513 with a rod-like mesogen, 8CB, show a conventional B4 phase, in which distinct left- and right-handed chiral domains with opposite optical activity are observed. The optical behavior of the mixtures is consistent with NMR results, which show a splitting of the carbonyl peak of the bent-core molecules into two, indicating a twisted conformation between the two molecular arms of the bent-core molecules as in conventional B4 materials.

Diastereomeric liquid crystal domains at the mesoscale.

In many technologies used to achieve separation of enantiomers, chiral selectors are designed to display differential affinity for the two enantiomers of a chiral compound. Such complexes are diastereomeric, differing in structure and free energy for the two enantiomers and enabling chiral discrimination. Here we present evidence for strong diastereomeric interaction effects at the mesoscale, manifested in chiral liquid crystal guest materials confined in a chiral, nanoporous network of semi-crystalline helical nanofilaments. The nanoporous host is itself an assembly of achiral, bent-core liquid crystal molecules that phase-separate into a conglomerate of 100 micron-scale, helical nanofilament domains that differ in structure only in the handedness of their homogeneous chirality. With the inclusion of a homochiral guest liquid crystal, these enantiomeric domains become diastereomeric, exhibiting unexpected and markedly different mesoscale structures and orientation transitions producing optical effects in which chirality has a dominant role.

Homeotropic orientation of a nematic liquid crystal by bent-core molecules adsorbed on its surface

We reported the promotion of a homeotropic alignment of a nematic liquid crystal (NLC) by bent-core liquid-crystal (BLC) Molecules adsorbed its surface. The BLC was mixed at various concentrations with the NLC, and the mixtures were injected into an empty cell with a cell gap of 13 μm. Although the pure NLC showed a heterogeneous orientation, the BLC-NLC mixture was gradually transformed to a homeotropic alignment with increasing concentration of the BLC. We investigated the surface topography of the samples by using an atomic force microscopy (AFM) and found that the BLC molecules were segregated into a polyimide (PI) surface and formed protrusion domains with diameters of 50−100 nm. The BLC protrusions might promote the homeotropic orientation of the NLC molecules.

Elimination of image flicker in fringe-field switching liquid crystal display driven with low frequency electric field.

Recently, a low frequency driving of a fringe-field switching-liquid crystal display (FFS-LCD) draws much attention to minimize the power consumption. In the low frequency driving of FFS-LCD, an image flickering effect occurs when the sign of the electric field is reversed. We suggested a method to eliminate the image flickering effect by doping small amount of bent-core liquid crystal (BLC) molecules. The BLC molecules have an opposite sign of flexoelectric polarization and reduce the flexoelectric polarization of the host liquid crystal. By adding 2.0 wt% of BLC, the total transmittance during a positive and a negative electric field could be balanced and the image flickering effect was not observed by eyes.

Synthesis and structure of lateral halogenated V-shaped liquid crystal molecules based on a 1,7-naphthalene central core and alkylthio tails

A series of small angle bent-core (V-shaped) mesogens carrying 1,7-naphthalene as a central core linked with lateral halogenated (chlorinated or fluorinated) Schiff-base side wings and alkylthio terminal tails of variable carbon number (n = 12, 16) was synthesised in order to reduce the transition temperature and improve the phase stability of bent-core liquid crystal molecules. Differential scanning calorimetry (DSC), polarising optical microscopy (POM), small-angle X-ray scattering system (SAXS) and two-dimensional X-ray diffractometer were applied to ascertain the mesomorphic structure and phase transition temperatures of the compounds. The results confirm that all the molecules show thermotropic liquid crystalline behaviour and exhibit hexagonal columnar phase (Colh) in a certain temperature range. Compared with the homologous compounds without lateral halogen, the cleaning point temperature of lateral halogenated V-shaped compounds generally decrease and the Colh phase ranges are more extensive. The influence of lateral chlorine on the cleaning point temperature is more obvious, as well as the effect of lateral fluorine on the range of Colh phase.

Alignment of nematic liquid crystals by a bent-core substrate

Monolayers composed of bent-core liquid crystal molecules have recently been investigated in regard to a possible alignment method for bulk bent-core liquid crystal phases. This paper examines the use of a bent-core monolayer to align nematic liquid crystal phases, which are also used for optical detection of substrate orientation in many applications. Atomistic molecular dynamics simulation is used to gain an understanding at the molecular level of how the nematic liquid crystals are aligned by the monolayer. The nematic liquid crystal molecules preferentially enter the bent-core monolayer, and take on the orientation of the upper arm of the bent-core molecules in the layer. These results suggest that nematic liquid crystal phases can be aligned by a bent-core substrate.

Interface structure of the dark conglomerate liquid crystal phase

The dark conglomerate (DC) phase is the spontaneously chiral, isotropic fluid formed by achiral bent-core liquid crystal molecules characterized by well-defined local smectic liquid crystal layering deformed into a disordered “plumber's nightmare” array of 100 nm-scale, focal conic-like domains. Here we report the interface structure of this phase, showing that surface confinement orders the focal conics into a hexagonal plumber's nightmare lattice, directly confirming the topology proposed for the DC phase. The observations suggest that a bulk phase of saddle–splay dominated focal conics may be produced in DC materials under suitable conditions, which opens the way for the development of two-dimensional or even three-dimensional periodic dielectric media for photonic crystal applications.

Optical waveguiding in bent-core liquid-crystal filaments

We demonstrate optical waveguiding in recently discovered free-standing bent-core liquid-crystal filaments. The bent-core liquid-crystal molecules in air self-assemble into a cylindrical geometry that is "solidlike" along the radial direction of the filament and liquid in the axial direction of the filament. These filaments are unique not only because they are fluids, but also because they are anisotropic. For this reason, their waveguiding properties not predictable need to be characterized. The light power transmitted through the filament was found to be independent of temperature from 180 degrees C to near room temperature. Initial defects of newly pulled filaments were found to self-anneal, thus leaving defect-free fibers, where light scattering was found to be insignificant. The absorbance was found to be strongly wavelength dependent in the visible regime and relatively small in the infrared range. A self-assembled optical waveguide with self-annealing fluid properties may have promising applications in optical communications or in optical microchips.

Theory of bent-core liquid-crystal phases and phase transitions.

We study phases and phase transitions that can take place in the recently discovered bow-shaped or bent-core liquid-crystal molecules. We show that to completely characterize phases exhibited by such bent-core molecules a third-rank tensor T(ijk) order parameter is necessary in addition to the vector and the nematic (second-rank) tensor order parameters. We present an exhaustive list of possible liquid phases, characterizing them by their space-symmetry group and order parameters, and catalog the universality classes of the corresponding phase transitions that we expect to take place in such bent-core molecular liquid crystals. In addition to the conventional liquid-crystal phases such as the nematic phase, we predict the existence of other liquid phases, including the spontaneously chiral nematic (N(T)+2)(*) and chiral polar (V(T)+2)(*) phases, the orientationally ordered but optically isotropic tetrahedratic T phase, and a nematic N(T) phase with D(2d) symmetry that is neither uniaxial nor biaxial. Interestingly, the isotropic-tetrahedratic transition is continuous in mean-field theory, but is likely driven first order by thermal fluctuations. We conclude with a discussion of smectic analogs of these phases and their experimental signatures.

Biaxial model of the surface anchoring of bent-core smectic liquid crystals.

In synclinically tilted smectic phases, bent-core liquid crystal molecules aligned with the director in the plane of a cell boundary will, in general, have their molecular (bow) planes parallel to the boundary, normal to it, or at a well-defined intermediate orientation. A model describing the interaction of such bent-core (banana-shaped) molecules with planar surfaces that distinguishes energetically between molecules lying flat on the surface and those oriented edge on is given by a biaxial modification of the uniaxial surface anchoring expression used for chiral smectics of rod-shaped molecules. When combined with a field-induced straightening of the smectic layers, the model provides a mechanism for the transition from an analog to a bistable director response observed electro-optically in the ferroelectric banana-shaped material (R,S)-MHOBOW.