Nematic Liquid Crystalline Phase Research Articles

Spontaneous chiral symmetry breaking in polar fluid–heliconical ferroelectric nematic phase

Spontaneous mirror symmetry breaking by formation of chiral structures from achiral building blocks and emergent polar order are phenomena rarely observed in fluids. Separately, they have both been found in certain nematic liquid crystalline phases; however, they have never been observed simultaneously. Here, we report a heliconical arrangement of achiral molecules in the ferroelectric nematic phase. The phase is thus spontaneously both polar and chiral. Notably, the pitch of the heliconical structure is comparable to the wavelength of visible light, giving selective reflection controllable by temperature or application of a weak electric field. Despite bearing resemblance to the heliconical twist-bend nematic phase, this chiral ferroelectric nematic phase arises from electrical interactions that induce a noncollinear orientation of electric dipoles.

Structural Study of Nematogenic Compound 5OS5

The S-(4-pentylphenyl) 4-(pentyloxy)benzothioate, forming the nematic phase, is investigated by X-ray diffraction in temperatures between 263 K and 365 K, with the support of differential scanning calorimetry and polarizing optical microscopy. The microscopic observations show changes within the solid state, while X-ray diffraction does not indicate any transitions between the crystal phases. The Rietveld refinement shows that the crystal phase formed from the melt is the same monoclinic crystal phase with the P21/c space group as reported for a single crystal grown from an ethanol solution. The temperature dependence of the unit cell parameters in the 263–335 K range is determined and the coefficients of thermal expansion are obtained. The unit cell expands on heating along the longer ac-diagonal and b-axis while, along the shorter ac-diagonal, a very small shrinkage occurs. The diffraction patterns of the liquid crystalline nematic phase indicate the formation of dimers via hydrogen bonding. Density functional theory calculations (def2TZVPP basis set, B3LYP-D3(BJ) correlation-exchange functional) are applied for geometry optimization of an isolated molecule and selected dimers.

Investigating the phase behaviour of binary suspensions of cellulose nanocrystals and montmorillonite with nonlinear rheology, SAXS and polarized optical microscopy

Using microscopy imaging techniques, X-ray scattering, and nonlinear rheological measurements, we have examined microstructural changes, and phase behavior of cellulose nanocrystals (CNC)/montmorillonite (MMT) composite colloidal systems. Fourier-transform (FT) rheology-stress decomposition methods, Lissajous-Bowditch plots, and other techniques are used to both qualitatively and quantitatively determine the various phases that the suspensions exhibit. In the MAOS (medium amplitude oscillatory shear) region, multiple scaling regions, as well as quadratic scaling regions are obtained. The dependence of the normalized third relative intensity (I3/1) values on angular frequency (ω) also provided new insights into how nonlinear parameters depend on the various CNC/MMT phases. These findings allow us to differentiate various phases exhibited by the composite system, including the isotropic, biphasic, and chiral nematic liquid crystalline (LC) phases. The CNC/MMT nanocomposite system exhibits a variety of liquid crystalline phases, which may contribute to improved mechanical properties for the system, including increased mixture strength, stiffness, and toughness because of the particle alignment in the LC phase. Additionally, the field of optics and photonics may find use for this nanocomposite system in the fabrication of sensors, polarizers, and optical films; energy storage applications where the aligned structures facilitate ion transport; and the formulation of paints and coatings where the strain stiffening and shear thinning behavior of the CNC/MMT composite system are critical.

Splay-induced order in systems of hard tapers.

The main objective of this work is to clarify the role that taper-shaped elongated molecules, i.e., molecules with one end wider than the other, can play in stabilizing orientational order. The focus is exclusively on entropy-driven self-organization induced by purely excluded volume interactions. Drawing an analogy to RM734 (4-[(4-nitrophenoxy)carbonyl]phenyl-2,4-dimethoxybenzoate), which is known to stabilize ferroelectric nematic (N_{F}) and nematic splay (N_{S}) phases, and assuming that molecular biaxiality is of secondary importance, we consider monodisperse systems composed of hard molecules. Each molecule is modeled using six collinear tangent spheres with linearly decreasing diameters. Through hard-particle, constant-pressure Monte Carlo simulations, we study the emergent phases as functions of the ratio between the smallest and largest diameters of the spheres (denoted as d) and the packing fraction (η). To analyze global and local molecular orderings, we examine molecular configurations in terms of nematic, smectic, and hexatic order parameters. Additionally, we investigate the radial pair distribution function, polarization correlation function, and the histogram of angles between molecular axes. The last characteristic is utilized to quantify local splay. The findings reveal that splay-induced deformations drive unusual long-range orientational order at relatively high packing fractions (η>0.5), corresponding to crystalline phases. When η<0.5, only short-range order is affected, and in addition to the isotropic liquid, only the standard nematic and smectic-A liquid crystalline phases are stabilized. However, for η>0.5, apart from the ordinary nonpolar hexagonal crystal, three additional frustrated crystalline polar blue phases with long-range splay modulation are observed: antiferroelectric splay crystal (Cr_{S}P_{A}), antiferroelectric double-splay crystal (Cr_{DS}P_{A}), and ferroelectric double-splay crystal (Cr_{DS}P_{F}). Finally, we employ Onsager-Parsons-Lee local density functional theory to investigate whether any sterically induced (anti)ferroelectric nematic or smectic-A type of ordering is possible for our system, at least in a metastable regime.

Charge-driven liquid-crystalline behavior of ligand-functionalized nanorods in apolar solvent.

Concentrated colloidal suspensions of nanorods often exhibit liquid-crystalline (LC) behavior. The transition to a nematic LC phase, with long-range orientational order of the particles, is usually well-captured by Onsager's theory for hard rods, at least qualitatively. The theory shows how the volume fraction at the transition decreases with increasing aspect ratio of the rods. It also explains that the long-range electrostatic repulsive interaction occurring between rods stabilized by their surface charge can significantly increase their effective diameter, resulting in a decrease in the volume fraction at the transition, as compared to sterically stabilized rods. Here, we report on a system of ligand-stabilized LaPO4 nanorods, of aspect ratio ≈11, dispersed in apolar medium exhibiting the counter-intuitive observation that the onset of nematic self-assembly occurs at an extremely low volume fraction of ≈0.25%, which is lower than observed (≈3%) with the same particles when charged-stabilized in polar solvent. Furthermore, the nanorod volume fraction at the transition increases with increasing concentration of ligands, in a similar way as in polar media where increasing the ionic strength leads to surface charge screening. This peculiar system was investigated by dynamic light scattering, Fourier-transform infrared spectroscopy, zetametry, electron microscopy, polarized light microscopy, photoluminescence measurements, and X-ray scattering. Based on these experimental data, we formulate several tentative scenarios that might explain this unexpected phase behavior. However, at this stage, its full understanding remains a pending theoretical challenge. Nevertheless, this study shows that dispersing anisotropic nanoparticles in an apolar solvent may sometimes lead to spontaneous ordering events that defy our intuitive ideas about colloidal systems.

Room temperature nematic liquid crystals: Synthesis and characterisation of pentabromophenol and cyanobiphenyl derived rod-shaped molecules

ABSTRACT Calamitic molecules consisting of pentabromophenol tethered to cyanobiphenyl via a flexible alkyl chain were synthesised and characterised for their mesomorphic properties. New chemical structures differing in the length of the spacer (6a–f) were confirmed by FT-IR, 1H-NMR and 13C-NMR spectroscopies, and by elemental analysis. Compounds having six, eight, nine and ten methylene units in the spacer show room-temperature nematic liquid crystalline phases and the other derivatives are soft solids. The mesomorphic behaviour and thermal stability of all compounds have been investigated by polarised optical microscopy, differential scanning calorimetry and thermal gravimetric analysis, respectively.

Chiral Chromonics Confined in Spherical Geometries

Chromonic liquid crystals have recently received a lot of attention due to their spontaneous self-assembly in supramolecular columnar structures that, depending on their concentration in water, align to form a nematic liquid crystalline phase. The chirality may be induced in chromonics by adding chiral moieties to the nematic phase or enhanced by confining them in curved geometrical constraints. This review summarizes the recent research developments on chiral chromonic liquid crystals confined in spherical geometry, relating the results to what was observed for thermotropic liquid crystals in the same conditions. The review focuses on the studies carried out on commercially available nematic chromonics, investigating the effects on their topologies in different anchoring conditions and different chiral dopants and suggesting an application in the sensor field.

Dielectric response of a ferroelectric nematic liquid crystalline phase in thin cells

ABSTRACT We studied the dielectric properties of a polar nematic phase (NF) sandwiched between two gold or ITO electrodes, serving as a cell surface. In bulk, NF is expected to exhibit a Goldstone mode (phason), because polarisation can uniformly rotate with no energy cost. However, because the coupling between the direction of nematic director and polarisation is finite, and the confinement, even in the absence of the aligning surface layer, induces some energy cost for a reorientation of polarisation, the relaxation frequency of the phason mode is measured in a kHz regime. The phason mode is easily quenched by a bias electric field, which enables fluctuations in the magnitude of polarisation to be followed in both the ferroelectric and paraelectric nematic phases. This amplitude (soft) mode is also influenced by boundary conditions. A theory describing the phase and amplitude fluctuations in the NF phase shows that the free energy of the system and, consequently, the dielectric response are dominated by polarisation-related terms with the flexoelectricity being relevant only at a very weak surface anchoring. Contributions due to the nematic elastic terms are always negligible. The model relates the observed low-frequency mode to the director fluctuations weakly coupled to polarisation fluctuations.

3D printing of responsive chiral photonic nanostructures

Finely controlled flow forces in extrusion-based additive manufacturing can be exploited to program the self-assembly of malleable nanostructures in soft materials by integrating bottom-up design into a top-down processing approach. Here, we leverage the processing parameters offered by direct ink-writing (DIW) to reconfigure the photonic chiral nematic liquid crystalline phase in hydroxypropyl cellulose (HPC) solutions prior to deposition on the writing substrate to direct structural evolution from a particular initial condition. Moreover, we incorporate polyethylene glycol (PEG) into iridescent HPC inks to form a physically cross-linked network capable of inducing kinetic arrest of the cholesteric/chiral pitch at length scales that selectively reflect light throughout the visible spectrum. Based on thorough rheological measurements, we have found that printing the chiral inks at a shear rate where HPC molecules adopt pseudonematic state results in uniform chiral recovery following flow cessation and enhanced optical properties in the solid state. Printing chiral inks at high shear rates, on the other hand, shifts the monochromatic appearance of the extruded filaments to a highly angle-dependent state, suggesting a preferred orientation of the chiral domains. The optical response of these filaments when exposed to mechanical deformation can be used in the development of optical sensors.

Mesogenic Groups Control the Emitter Orientation in Multi‐Resonance TADF Emitter Films**

AbstractThe use of thermally activated delayed fluorescence (TADF) emitters and emitters that show preferential horizontal orientation of their transition dipole moment (TDM) are two emerging strategies to enhance the efficiency of OLEDs. We present the first example of a liquid crystalline multi‐resonance TADF (MR‐TADF) emitter, DiKTa‐LC. The compound possesses a nematic liquid crystalline phase between 80 °C and 110 °C. Importantly, the TDM of the spin‐coated film shows preferential horizontal orientation, with an anisotropy factor, a, of 0.28, which is preserved in doped poly(vinylcarbazole) films. Green‐emitting (λEL=492 nm) solution‐processed OLEDs based on DiKTa‐LC showed an EQEmax of 13.6 %. We thus demonstrate for the first time how self‐assembly of a liquid crystalline TADF emitter can lead to the so‐far elusive control of the orientation of the transition dipole in solution‐processed films, which will be of relevance for high‐performance solution‐processed OLEDs.

Mesogenic Groups Control the Emitter Orientation in Multi-Resonance TADF Emitter Films.

The use of thermally activated delayed fluorescence (TADF) emitters and emitters that show preferential horizontal orientation of their transition dipole moment (TDM) are two emerging strategies to enhance the efficiency of OLEDs. We present the first example of a liquid crystalline multi-resonance TADF (MR-TADF) emitter, DiKTa-LC. The compound possesses a nematic liquid crystalline phase between 80 °C and 110 °C. Importantly, the TDM of the spin-coated film shows preferential horizontal orientation, with an anisotropy factor, a, of 0.28, which is preserved in doped poly(vinylcarbazole) films. Green-emitting (λEL =492 nm) solution-processed OLEDs based on DiKTa-LC showed an EQEmax of 13.6 %. We thus demonstrate for the first time how self-assembly of a liquid crystalline TADF emitter can lead to the so-far elusive control of the orientation of the transition dipole in solution-processed films, which will be of relevance for high-performance solution-processed OLEDs.

Molecular spectroscopy and optical effect of Albendazole chemical compound behaves as liquid crystal: A theoretical and experimental approach

In the present work, we have investigated the Albendazole (ABZ) molecule which behaves as a liquid crystal or mesophase under the impact of temperature as well as the external effect of the electric field. Under the electric field's impact, the ABZ molecule demonstrates the mesophase phase stability in order parameter, birefringence, director angle and refractive index. At the higher temperature, the ABZ molecule shifted to the mesophase. Theoretical IR spectrosctrum of the ABZ molecule has been correlated with the experimental evidence. The XRD pattern of ABZ at 250 °C exhibits crystalline nature and at higher temperatures (300 °C and 400 °C) it reveal the amorphous nature. Tauc plots indicate optical bandgaps 4.73, 1.38, 6.02 and 5.80 eV at room temperature, 250 °C, 300 °C and 400 °C, respectively. Such variations in bandgap indicate self-organizing characteristic of the nematic liquid crystalline phase in the sample. FESEM images at higher temperatures exhibit pores with various structures in the ABZ.

Development of Hydrogen-Bonded Dimer-Type Photoluminescent Liquid Crystals of Fluorinated Tolanecarboxylic Acid

Functional molecules possessing photoluminescence (PL) and liquid-crystalline (LC) behaviors, known as photoluminescent liquid crystals, along with a small molecular structure, have attracted significant attention. Fluorinated tolane skeletons are small π-conjugated structures, which are promising candidates for such functional molecules. These structures were revealed to exhibit strong PL in solid state but no LC behavior. Based on a report on hydrogen-bonded dimer-type LC molecules of carboxylic acid, in this study, we designed and synthesized a series of fluorinated tolanecarboxylic acids (2,3,5,6-tetrafluoro-4-[2-(4-alkoxyphenyl)ethyn-1-yl]benzoic acids) as promising PLLC molecules. Evaluation of the LC behavior revealed that fluorinated tolanecarboxylic acids with a longer alkoxy chain than a butoxy chain exhibited nematic LC behavior. Additionally, fluorinated tolanecarboxylic acids showed intense PL in the solution and crystalline states. Notably, fluorinated tolanecarboxylic acid with an aggregated structure in the nematic LC phase also exhibited PL with a slight blue shift in PL maximum wavelength compared to the crystalline state. The present fluorinated tolanecarboxylic acid exhibiting PL and LC characteristics in a single molecule can be applied to thermoresponsive PL materials, such as a PL thermosensor.

Ethylenediaminetetraacetic acid-functionalized graphene oxide for fabrication of a strong laminated film by ionic cross-linking

Graphene oxide is functionalized with ethylenediaminetetraacetic acid groups to investigate the effect of ethylenediaminetetraacetic acid groups on its colloidal, assembly, and ionic cross-linking behaviors. Ethylenediaminetetraacetic acid-functionalized graphene oxide exhibits a high aqueous dispersibility for presenting a nematic liquid-crystalline phase which is an important factor for fabrication of the well-ordered laminated films. Ethylenediaminetetraacetic acid-graphene oxide films show a distinct internal structure from graphene oxide films owing to the heterogeneous surface of ethylenediaminetetraacetic acid-graphene oxide sheets composed of partially reduced and ethylenediaminetetraacetic acid decorated regions. In addition, the mechanical properties of ethylenediaminetetraacetic acid-graphene oxide films are more enhanced by ionic cross-linking with divalent cations, and their degree of mechanical enhancement is also more dependent on the type of cations than graphene oxide films. The interesting behaviors of ethylenediaminetetraacetic acid-graphene oxide suggest the ethylenediaminetetraacetic acid functionalization can greatly improve the potential of graphene oxide derivatives to develop a high-performance structural material.

Photophysical and thermophysical behavior of D-π-A-type fluorinated diphenylacetylenes bearing an alkoxy and an ethoxycarbonyl group at both longitudinal molecular terminals

Fluorinated diphenylacetylenes have recently attracted significant attention because they exhibit intense photoluminescence (PL) in the crystalline state owing to their electron-density distribution and the formation of H···F hydrogen bonds. In this study, fluorinated diphenylacetylenes bearing alkoxy and ethoxycarbonyl (COOEt) groups at both longitudinal molecular terminals were synthesized, and their photophysical and thermophysical behavior were evaluated, along with their structure–property relationship. The COOEt-substituted fluorinated diphenylacetylenes exhibited blue PL in the solution and crystalline states. Both the fluorine atom and the COOEt substituent play a crucial role in forming a large electron-density distribution and restricting the molecular motion of diphenylacetylenes through H···F and O···H hydrogen bonds in the crystalline state. The alkoxy-chain length of the fluorinated diphenylacetylenes not only affected their PL behavior in the crystalline state, but also their thermophysical behavior. Notably, fluorinated diphenylacetylenes with long alkoxy chains, such as heptyloxy and octyloxy chains, displayed a nematic liquid-crystalline (LC) phase. These findings facilitate the development of promising multifunctional molecules possessing PL and LC characteristics.

Crystal Structure of a 4,7-Bis(phenylethynyl)-2,1,3-benzothiadiazole-Based Cyclophane and the Mechanoresponsive Luminescence

Abstract The photophysical properties of luminescent cyclophanes have been traditionally examined in an isolated state in solution. In contrast, the behavior of luminescent cyclophanes in response to external stimuli in the solid state has not yet been fully understood. Herein, we report on the crystal structure of a cyclophane featuring one 4,7-bis(phenylethynyl)-2,1,3-benzothiadiazole group and its mechanochromic luminescence. Mechanical grinding of the crystals results in a phase transition to an amorphous state, which is concomitant with an emission color change from green to yellow. Annealing the amorphous phase at 100 °C induces a phase transition to another crystalline state, and green emission is observed again. On subsequent heating, the benzothiadiazole-based cyclophane forms a nematic liquid-crystalline phase above 191 °C. These results indicate that the introduction of π-extended planar luminophores within cyclic molecular structures is a promising approach for the design of stimuli-responsive luminescent materials.

Development of photoluminescent liquid-crystalline dimers bearing two fluorinated tolane-based luminous mesogens

Fluorinated tolane dimers consisting of two fluorinated tolanes connected by various lengths of an alkylene tether were designed and synthesized via three reaction steps including an aromatic nucleophilic substitution and a Mitsunobu-type etherification reaction. Although mesophases were not observed in the case of dimers connected by relatively short alkylene tethers, fluorinated tolane dimers with relatively long tethers underwent a transition to a nematic liquid crystalline (N LC) phase during cooling. In addition, the fluorinated tolane dimers exhibited photoluminescence (PL), both in solution and in the crystalline (Cr) phase, with efficiencies of up to 0.72. It is noteworthy that the PL behavior of the N phase molecular aggregates was found to be different from that of the Cr phase. These findings suggest a promising route for the development of thermo-responsive photoluminescent liquid crystals (PLLCs) and thermosensing applications of PL materials.

Investigation of Thermal-Induced Changes in Molecular Order on Photopolymerization and Performance Properties of a Nematic Liquid-Crystal Diacrylate.

Polymerization shrinkage and associated stresses are the main reasons for dental restorative failure. We developed a series of liquid crystal diacrylates and dimethacrylates which have markedly low polymerization shrinkage. In order to fully understand the effects of temperature-induced changes of molecular order on the photopolymerization process and performance properties of the generated polymers, the photopolymerization of a difunctional acrylate, 2-t-butyl-1,4-phenylene bis (4-(6-(acryloyloxy)hexyloxy)benzoate), which exists in the nematic liquid crystalline phase at room temperature, was investigated as a function of photopolymerization temperature over the nematic to isotropic range. Morphological studies suggested that a mesogenic phase was immediately formed in the polymer even if polymerization in thin films occurred above the nematic-to-isotropic (N→I) transition temperature of the monomer (Tn-i = 45.8 °C). Dynamic mechanical analysis of 2 × 2 mm cross-section bar samples polymerized at 60 °C showed reduced elastic moduli, increased glass transition temperature and formation of a more crosslinked network, in comparison to polymers formed at lower polymerization temperatures. Fractography analysis showed that polymers generated from the nematic liquid crystalline phase underwent a different fracture pattern in comparison to those generated from the isotropic phase. Volumetric shrinkage (2.2%) found in polymer polymerized from the nematic liquid crystalline phase at room temperature was substantially less than the 6.0% observed in polymer polymerized from an initial isotropic phase at 60 °C, indicating that an organized monomer can greatly contribute to reducing cure shrinkage.

Aspect ratio dependent viscoelastic properties of graphene oxide liquid crystals

We present a systematic investigation of the size-dependent viscoelastic properties of aqueous suspensions of graphene oxide (GO). The study is performed on three different size graphene oxide dispersions with an average sheet surface area of 22.89, 126.42 and 173.83 μm2. The viscoelastic properties of the GO suspensions are found to be strongly dependent on the size of GO sheets. Irrespective of the size, all the GO dispersions revealed an isotropic phase at low volume fractions and a nematic liquid crystalline phase above critical volume fractions. The formation of nematic liquid crystalline phase strongly depends on the size of GO sheets. The steady-state flow measurements confirmed the nematic liquid crystalline phase formation at a lower fraction (φ = 0.24%) for ultra-large GO sheet dispersion than small area graphene oxide dispersion (φ = 0.45%). Further, frequency sweep measurements of ultra-large GO suspension exhibit higher storage and loss moduli than small area graphene oxide dispersion for a particular GO concentration. The study also confirmed the gel-like phase formation at a higher GO fraction (φ > 0.73%), where both storage and loss moduli are nearly independent of frequency. The reported size-dependent viscoelastic properties of GO liquid crystals are very important for the fabrication of GO-based materials for various potential applications.

Long-time relaxation dynamics in nematic and smectic liquid crystals of soft repulsive colloidal rods.

Understanding the relaxation dynamics of colloidal suspensions is crucial to identifying the elements that influence the mobility of their constituents, assessing their macroscopic response across the relevant time and length scales, and thus disclosing the fundamentals underpinning their exploitation in formulation engineering. In this work, we specifically assess the impact of long-ranged ordering on the relaxation dynamics of suspensions of soft repulsive rodlike particles, which are able to self-organize into nematic and smectic liquid-crystalline phases. Rods are modeled as soft repulsive spherocylinders with a length-to-diameter ratio L^{★}=5, interacting via the truncated and shifted Kihara potential. By performing dynamic Monte Carlo simulations, we analyze the effect of translational and orientational order on the diffusion of the rods along the relevant directions imposed by the morphology of the background phases. To provide a clear picture of the resulting dynamics, we assess its dependence on temperature, which can dramatically determine the response time of the system relaxation and the self-diffusion coefficients of the rods. The computation of the van Hove correlation functions allows us to identify the existence of rods that diffuse significantly faster than the average and whose concentration can be accurately adjusted by a suitable choice of temperature.