Twist-Bend Nematic Glasses: The Synthesis and Characterisation of Pyrene-based Nonsymmetric Dimers

A selection of pyrene-based liquid crystal dimers have been prepared, containing either methylene-ether or diether linked spacers of varying length and parity. All the diether linked materials, CBOnO.Py (n=5, 6, 11, 12), exhibit conventional nematic and smectic A phases, with the exception of CBO11O.Py which is exclusively nematic. The methylene-ether linked dimer, CBnO.Py, with an even-membered spacer (n=5) was solely nematogenic, but odd-members (n=6, 8, 10) exhibited both nematic and twist-bend nematic phases. Replacement of the cyanobiphenyl fragment by cyanoterphenyl giving CT6O.Py, gave elevated melting and nematic-isotropic transition temperatures, and SmA and SmC_A phases were observed on cooling the nematic phase. Intermolecular face-to-face associations of the pyrene moieties drive glass formation, and all these materials have a glass transition temperature at or above room temperature. The stability of the glassy twist-bend nematic phase allowed for its study using AFM, and the helical pitch length, P_TB, was measured as 6.3 and 6.7 nm for CB6O.Py and CB8O.Py, respectively. These values are comparable to the shortest pitch of a twist-bend nematic phase measured to date.     

Intrinsically Chiral Twist-Bend Nematogens: Interplay of Molecular and Structural Chirality in the NTB Phase

The front cover artwork is provided by Dr Rebecca Walker of the Liquid Crystals Group at the University of Aberdeen. The image is a cartoon depiction of the formation of the heliconical chiral twist-bend nematic phase (N*_TB) from its constituent bent molecules. The presence of a single enantiomer of the chiral, lactate-based liquid crystal dimers biases the formation of helices with only one handedness, unlike in the conventional N_TB phase, observed for achiral molecules, for which the left- and right-handed helices are doubly degenerate. Read the full text of the Research Article at 10.1002/cphc.202200807 .     

A Ten-Year Perspective on Twist-Bend Nematic Materials

The discovery of the twist-bend nematic phase (N_TB) is a milestone within the field of liquid crystals. The N_TB phase has a helical structure, with a repeat length of a few nanometres, and is therefore chiral, even when formed by achiral molecules. The discovery and rush to understand the rich physics of the N_TB phase has provided a fresh impetus to the design and characterisation of dimeric and oligomeric liquid crystalline materials. Now, ten years after the discovery of the N_TB phase, we review developments in this area, focusing on how molecular features relate to the incidence of this phase, noting the progression from simple symmetrical dimeric materials towards complex oligomers, non-covalently bonded supramolecular systems.     

A Twist‐Bend Nematic (NTB) Phase of Chiral Materials

New chiral dimers consisting of a rod‐like and cholesterol mesogenic units are reported to form a chiral twist‐bend nematic phase (N_TB*) with heliconical structure. The compressibility of the N_TB phase made of bent dimers was found to be as large as in smectic phases, which is consistent with the nanoperiodic structure of the N_TB phase. The atomic force microscopy observations in chiral bent dimers revealed a periodicity of about 50 nm, which is significantly larger than the one reported previously for non‐chiral compounds (ca. 10 nm).     

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 Switching of the Circularly Polarized Luminescence of Disubstituted Polyacetylene by Selective Transmission through a Thermotropic Chiral Nematic Liquid Crystal

The circularly polarized luminescence (CPL) of chiral disubstituted liquid‐crystalline polyacetylene (di‐LCPA) can be dynamically switched and amplified from left‐ to right‐handed CPL and vice versa through the selective transmission of CPL across a thermotropic chiral nematic liquid crystal (N*‐LC) phase. By combining a chiral di‐LCPA CPL‐emitting film with an N*‐LC cell and tuning the selective reflection band of the N*‐LC phase to coincide with the CPL emission band, a CPL‐switchable cell was constructed. The phase change induced by the thermotropic N*‐LC cell by varying the temperature leads to a change in the selective transmission of CPL, which enables the dynamic switching and amplification of CPL. It is anticipated that CPL‐switchable devices might find applications in switchable low‐threshold lasers and optical memory devices.     

The NTB phase in an achiral asymmetrical bent-core liquid crystal terminated with symmetric alkyl chains

ABSTRACT

The characteristics of the twist-bend nematic (N_TB) phase of an achiral asymmetrical rigid bent-core liquid crystal (LC), the ends of which are terminated by symmetric alkyl chains, are reported. The nematic–nematic phase transition and its properties are studied by differential scanning calorimetry (DSC), polarising microscopy and the electro-optic techniques. Large domains of opposite handedness are observed in the absence of the external field in the N_TB phase. Another set of periodic striped pattern consisting of domains with sharp boundaries is formed when a high-frequency electric field with a magnitude above its threshold is applied across a planarly aligned cell. The neighbouring domains are of opposite chirality. The temperature dependence of the heliconical angle θ₀ is determined from the birefringence measurements using Haller’s extrapolation technique. This material shows lower values of the heliconical angle (~9.3° at a temperature of 155°C within the N_TB phase) when compared with the previously reported dimer-based twist-bend nematic LCs (31°±3°).     

Utilising Saturated Hydrocarbon Isosteres of para Benzene in the Design of Twist-Bend Nematic Liquid Crystals

The nematic twist-bend (N_TB) liquid crystal phase possesses a local helical structure with a pitch length of a few nanometres and is the first example of spontaneous symmetry breaking in a fluid system. All known examples of the N_TB phase occur in materials whose constituent mesogenic units are aromatic hydrocarbons. It is not clear if this is due to synthetic convenience or a bona fide structural requirement for a material to exhibit this phase of matter. In this work we demonstrate that materials consisting largely of saturated hydrocarbons can also give rise to this mesophase.     

Two‐Dimensional Skyrmion Lattice Formation in a Nematic Liquid Crystal Consisting of Highly Bent Banana Molecules

We synthesized a novel banana‐shaped molecule based on a 1,7‐naphthalene central core that exhibits a distinct mesomorphism of the nematic‐to‐nematic phase transition. Both the X‐ray profile and direct imaging of atomic force microscopy (AFM) investigations clearly indicates the formation of an anomalous nematic phase possessing a two‐dimensional (2D) tetragonal lattice with a large edge (ca. 59 Å) directed perpendicular to the director in the low‐temperature nematic phase. One plausible model is proposed by an analogy of skyrmion lattice in which two types of cylinders formed from left‐ and right‐handed twist‐bend helices stack into a 2D tetragonal lattice, diminishing the inversion domain wall.     

Mesomorphic Characteristics of Induced Chiral Nematic Phase of [Smectic LCP,PS(4BC/DM)/Nematic LC,E7/Chiral Dopant,CB-15]-Ternary Composite System

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Induced Circular Dichroism of Chiral Nematic Cellulose Films

Colloidal chiral nematic suspensions of cellulose were prepared from dissolving grade wood pulp. On evaporation of the water, the suspension dries down to give iridescent cellulose films. The optical properties of the films may be characterized by incorporating dyes in the films, and following the ordering of the dye molecules by measurement of induced circular dichroism (ICD). Structural changes to the films, such as decreasing the chiral nematic pitch by increasing the salt content and increasing the chiral nematic order through magnetic alignment, can be monitored by measuring the changes in ICD.     

Chiral and orientationally ordered fluid mesophases formed by oxadiazole bisaniline based achiral bent mesogens

Development of new liquid crystalline materials exhibiting interesting properties and phases continues to be an enabling enterprise in the forward march of their successful display and non-display applications. The design and synthesis of a homologous series of liquid crystalline bent-core compounds derived from the oxadiazole bisaniline moiety and the phase behavior of three members of the series that exhibit nematic, smectic C, and dark conglomerate phases is reported. The liquid crystalline phases exhibited by these mesogens are characterized using polarized optical microscopy, differential scanning calorimetry and x-ray scattering techniques. All three homologs prepared exhibit the nematic phase. Interestingly, the homolog with short hexyl terminal chains exhibits only the nematic phase that is stable over a very broad, nearly 100 K wide, temperature range. The compound with terminal octyl chains shows the chiral dark conglomerate phase below the nematic phase despite the bent molecules being achiral. The homolog with dodecyl alkyl chains is found to possess the smectic-C and two additional lamellar phases besides the nematic phase. These compounds enrich the library of achiral bent-core materials capable of exhibiting chiral and nematic phases.     

Chirality Induction through Nano‐Phase Separation: Alternating Network Gyroid Phase by Thermotropic Self‐Assembly of X‐Shaped Bolapolyphiles

The single gyroid phase as well as the alternating double network gyroid, composed of two alternating single gyroid networks, hold a significant place in ordered nanoscale morphologies for their potential applications as photonic crystals, metamaterials and templates for porous ceramics and metals. Here, we report the first alternating network cubic liquid crystals. They form through self‐assembly of X‐shaped polyphiles, where glycerol‐capped terphenyl rods lie on the gyroid surface while semiperfluorinated and aliphatic side‐chains fill their respective separate channel networks. This new self‐assembly mode can be considered as a two‐color symmetry‐broken double gyroid morphology, providing a tailored way to fabricate novel chiral structures with sub‐10 nm periodicities using achiral compounds.     

Modulated nematic structures and chiral symmetry breaking in 2D

ABSTRACT

We have studied the properties of biaxial particles interacting via an anisotropic pair potential, involving second-rank quadrupolar and third-rank octupolar coupling terms, using Monte Carlo simulation. The particles occupy the sites of a 2D square lattice and the interactions are restricted to nearest neighbours. The system exhibits spontaneous chiral symmetry breaking from an isotropic phase to a chiral modulated nematic phase, composed of ambidextrous chiral domains. When twofold axes of quadrupolar and octupolar tensors coincide this modulated phase appears to be the ambidextrous cholesteric phase with pitch comparable to a few lattice spacings. The associated phase transition is first order.     

Nematic Phase of Polar Unsymmetrical Bent-Core Molecules

In liquid crystalline systems, the presence of polar groups at lateral or terminal positions is fundamentally and technologically important. Bent-core nematics composed of polar molecules with short rigid cores usually exhibit highly disordered mesomorphism with some ordered clusters that favourably nucleate within. Herein, we have systematically designed and synthesized two new series of highly polar bent-core compounds comprised of two unsymmetrical wings, highly electronegative −CN and −NO₂ groups at one end, and flexible alkyl chains at the other end. All the compounds showed a wide range of nematic phases composed of cybotactic clusters of smectic-type (N_cyb). The birefringent microscopic textures of the nematic phase were accompanied by dark regions. Further, the cybotactic clustering in the nematic phase was characterized via temperature-dependent XRD studies and dielectric spectroscopy. Besides, the birefringence measurements demonstrated the ordering of the molecules in the cybotactic clusters upon lowering the temperature. DFT calculations illustrated the favourable antiparallel arrangement of these polar bent-core molecules as it minimizes the large net dipole moment of the system.     

Polymer and Mesoporous Silica Microspheres with Chiral Nematic Order from Cellulose Nanocrystals

Polymer microspheres with chiral nematic order were obtained from an emulsion polymerization technique using cellulose nanocrystals (CNCs) as the template. The growth of the liquid crystals from tiny tactoids to droplets with spherical symmetry was captured and investigated by both optical and electron microscopy for the first time. The size of the microspheres could be tuned between tens and hundreds of micrometers; to obtain single, integrated chiral nematic kernels, the size of water droplets in the emulsion should be similar to that of CNC tactoids. Through a double‐matrix templating method, novel silica microspheres with chiral nematic order were fabricated, which showed a high surface area and mesoporosity. The methods developed here may help to reveal the evolution of other self‐assembling systems, and these materials have potential applications in optical devices and chiral separations.     

A Nanohelicoidal Nematic Liquid Crystal Formed by a Non‐Linear Duplexed Hexamer

The twist‐bend modulated nematic liquid‐crystal phase exhibits formation of a nanometre‐scale helical pitch in a fluid and spontaneous breaking of mirror symmetry, leading to a quasi‐fluid state composed of chiral domains despite being composed of achiral materials. This phase was only observed for materials with two or more mesogenic units, the manner of attachment between which is always linear. Non‐linear oligomers with a H‐shaped hexamesogen are now found to exhibit both nematic and twist‐bend modulated nematic phases. This shatters the assumption that a linear sequence of mesogenic units is a prerequisite for this phase, and points to this state of matter being exhibited by a wider range of self‐assembling structures than was previously envisaged. These results support the double helix model of the TB phase as opposed to the simple heliconical model. This new class of materials could act as low‐molecular‐weight surrogates for cross‐linked liquid‐crystalline elastomers.     

Multiple Polar and Non-polar Nematic Phases

Liquid-crystal materials exhibiting up to three nematic phases are reported. Dielectric response measurements show that while the lower temperature nematic phase has ferroelectric order and the highest temperature nematic phase is apolar, the intermediate phase has local antiferroelectric order. The modification of the molecular structure by increasing the number of lateral fluorine substituents leads to one of the materials showing a direct isotropic-ferronematic phase transition.