Nematic Phase Research Articles

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers.

Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT-TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H-C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties. Thermotropic liquid crystalline (LC) behavior is confirmed by cross-polarized optical microscopy (CPOM) and closely correlated with multiple thermal transitions observed by differential scanning calorimetry (DSC). This LC behavior allows us to develop and utilize a thermal annealing treatment that results in thin films with notable long-range order, as shown by grazing-incidence X-ray diffraction (GIXD). Specifically, we identified a first LC phase, ranging from 218 °C to 107 °C, as a nematic phase featuring preferential face-on π-π stacking and edge-on lamellar stacking exhibiting a large extent of disorder and broad orientation distribution. A second LC phase is observed from 107 °C to 48 °C, as a smectic A phase featuring sharp, highly ordered out-of-plane lamellar stacking features and sharp tilted backbone stacking peaks, while the structure of a third LC phase with a transition at 48 °C remains unclear, but resembles that of the solid state at ambient temperature. Furthermore, the significance of thermal annealing is evident in the ∼3-fold enhancement of the electrical conductivity of ferric tosylate-doped annealed films reaching 55 S cm-1. More importantly, thermally annealed TPT-TT films exhibit both a narrow distribution of charge-carrier mobilities (1.4 ± 0.1) × 10-2 cm2 V-1 s-1 along with a remarkable device yield of 100% in an organic field-effect transistor (OFET) configuration. This molecular design approach to obtain highly ordered conjugated polymers in the solid state affords a deeper understanding of how intramolecular interactions and repeat-unit symmetry impact liquid crystallinity, solution aggregation, solution to solid-state transformation, solid-state morphology, and ultimately device applications.

Dielectric properties of liquid crystals

In the paper, dielectric properties of liquid crystals, especially the nematic phase, arediscussed. An outline of the development of theories describing these properties is presented. Thestatic theory of dielectric permittivity of anisotropic nematic liquid crystals on Onsager, Maier andMeier approach is discussed in details. In this view, anisotropic properties of dielectric permittivityof nematics as well parameters describing these properties are presented.Keywords: material science, liquid crystals, nematics, dielectric permittivity, electron polarisability,constant and induced dipole moment of molecule, vectors of electric field intensity, induction andpolarisation in nematic phase.

Influence of Electric Field on the Spectroscopic and Opto-electronic Properties of 10ABP: A DFT Study

Abstract: In this work, the terahertz (THz) frequency broad-range nematic phase stability under the effect of an external electric field is examined. Under the influence of an external electric field, the liquid crystal (LC) molecule 4-deca-alkylamino-4'-cyanobiphenyl (10ABP) has unfavourable or negative order characteristics. Under THz frequency, the nematic phase is stable in the electro-optical properties of refractive index, birefringence, director angle and order parameter under the influence of an external electric field, whereas the smectic phase exhibited nonstable behaviour (tilted stage). Even though the electro-optical parameter fluctuates at higher electric fields, the isotropic phase maintains its stability. The chemical transition state of the 10ABP LC molecule is more suited for the compound's reaction process. The 10ABP LC is also excellent for conducting applications because of its modest band gap.

Preparation and characterization of Schiff base and its complex with Cu(II) and study of their liquid crystalline properties.

The research includes the preparation of ligand E-H, and it was identified by spectroscopic methods Infra Red IR, Nuclear magnatic Reasonance NMR, Mass spectra· It was also prepared from the ligand a complexes with copper (11) and characterized by Infra Red spectra. Central metals ions and Schif base coordinated via O and N donor sites which was observed from IR spectra. The liquid crystal characteristics of the ligand was studied using polarized optical microscope POM and the ligand is a liquid crystal by showed nematic phase only, while no liquid crystal phase was detected in the prepared complex, and it disintegrated at 250°C.

Critical Percolation in the Ordering Kinetics of Twisted Nematic Phases.

I report on the experimental confirmation that critical percolation statistics underlie the ordering kinetics of twisted nematic phases in the Allen-Cahn universality class. Soon after the ordering starts from a homogeneous disordered phase and proceeds toward a broken Z_{2}-symmetry phase, the system seems to be attracted to the random percolation fixed point at a special timescale t_{p}. At this time, exact formulas for crossing probabilities in percolation theory agree with the corresponding probabilities in the experimental data. The ensuing evolution for the number density of hull-enclosed areas is described by an exact expression derived from a percolation model endowed with curvature-driven interface motion. Scaling relation for hull-enclosed areas versus perimeters reveals that the fractal percolation geometry is progressively morphed into a regular geometry up to the order of the classical coarsening length. In view of its universality and experimental possibilities, the study opens a path for exploring percolation keystones in the realm of nonequilibrium, phase-ordering systems.

Effects of polar end group, flexible spacer length and molecular conformation on properties of the liquid crystal dimers

ABSTRACT Two series of symmetric liquid crystal dimers, namely 1F and 3F, have been synthesised by varying the length of the flexible odd spacer. The melting temperatures and clear points of the 3F series are higher than those of the 1F series. The 1F series only exhibits nematic phase, while the 3F series displays both smectic A and nematic phases. As the length of the flexible spacer increases, the dominance of the smectic phase becomes more pronounced. This phenomenon may be attributed to the combined effect by the polar end group CF3 and the long flexible spacer on the molecular conformation.

Mean-field theory approach to three-dimensional nematic phase transitions in microtubules.

Microtubules are dynamic intracellular fibers that have been observed experimentally to undergo spontaneous self-alignment. We formulate a three-dimensional (3D) mean-field theory model to analyze the nematic phase transition of microtubules growing and interacting within a 3D space, then make a comparison with computational simulations. We identify a control parameter G_{eff} and predict a unique critical value G_{eff}=1.56 for which a phase transition can occur. Furthermore, we show both analytically and using simulations that this predicted critical value does not depend on the presence of zippering. The mean-field theory developed here provides an analytical estimate of microtubule patterning characteristics without running time-consuming simulations and is a step towards bridging scales from microtubule behavior to multicellular simulations.

Properties of the uniaxial and biaxial nematic phases of the dodecyltrimethylammonium bromide/1-dodecanol/water lyotropic mixture including azo dye and drug molecules

ABSTRACT Lyotropic nematic phase properties of novel mixtures of dodecyltrimethylammonium bromide (DTMABr)/1-dodecanol (DDeOH)/water, doping with anionic azo dyes (amaranth and tartrazine) and a drug molecule disodium cromoglycate (cromolyn, DSCG), were investigated. The textures of the uniaxial and biaxial nematic phases were observed by polarizing optical microscopy (POM). Uniaxial-to-biaxial nematic phase transitions were determined from the temperature dependence of the birefringences via laser conoscopy. Partial phase diagrams of the mixtures were constructed as a function of concentrations of dyes and drug molecules by combining the POM and laser conoscopy results. Small-angle X-ray scattering (SAXS) was performed to evaluate micellar structure parameters. The results indicate that those dyes and drug molecules have a greater effect on (a) the nematic-nematic phase transition temperatures, (b) the biaxial-nematic phase-domain range in the partial phase diagrams, and (c) micelle-shape anisotropy, comparing to the addition of other conventional inorganic electrolyte ions. Furthermore, dye and drug molecules may be sequenced in the Hofmeister series of ions, considering the number of ionic groups in their molecular structures and also the chaotropic and/or kosmotropic degrees of the ionic groups. Since these molecules may have a resonance structure (e.g. DSCG), as a result of the existence of the aromatic parts in their structures, this resonance structure should be considered to investigate their effects on the stabilization of the lyotropic nematic phases.

Mesomorphic, magnetic and DFT studies of biphenyl-based molecule with various substituted anilines

ABSTRACT A new series of liquid crystals consisting of biphenyl unit connected to phenyl core system have been successfully prepared wherein various substituents X= OCH3, F, Cl, Br and I were introduced in the para position of the imine fragment while the length of terminal alkoxy chain of seven carbon atoms was intact. The mesomorphic and thermal studies by POM and DSC exhibit dominant enantiotropic nematic (N) phase. A relatively weak magnetism was detected with vibrating sample magnetometer (VSM) for compounds 3F and 3I at room temperature, wherein the magnetic strength of fluoro-substituted compound appeared stronger than the iodo-substituted compound. The connectivity between the substituents X and their kinetic stability associated with the changes in HOMO-LUMO energy gap value (ΔEgap) supports that the terminal substituents X have great influence on the ΔEgap which can be ascribed to the chemical activity of the compounds. Present study shows an increase in the ΔEgap from OCH 3 < I < Br < Cl < F, where the largest ΔEgap indicates high molecular kinetic stability and low chemical reactivity because adding electrons to high-lying LUMO is energetically unfavourable, resulting in disruption of the molecular packing and reduction of nematogenic, which were validated by DSC and POM.

Anopore confinement in the cyanobiphenyl-based liquid crystal dimer CB7CB. A dielectric study

ABSTRACT We report an experimental work on the liquid crystal dimer 1’’,7’-bis(4-cyanobiphenyl-4’-yl) heptane (CB7CB) confined to Anopore membranes. We have studied the behaviour of the dielectric relaxation modes in the isotropic (I), nematic (N) and twist-bend nematic (NTB) phases by broadband dielectric spectroscopy and compared to the results of the bulk sample. We have found that the strength of the components of the static dielectric permittivity for bulk and confined samples diminishes when cooling but, once in the NTB phase, those of the confined CB7CB tend to decrease in a slower rate compared to the ones of bulk CB7CB. This work is meant to play a humble tribute to the first report on a cyanobiphenyl-based LC in its 50th anniversary.

Resurgence of superconductivity and the role of dxy hole band in FeSe1−xTex

Iron-chalcogenide superconductors display rich phenomena caused by orbital-dependent band shifts and electronic correlations. Additionally, they are potential candidates for topological superconductivity due to the band inversion between the Fe d bands and the chalcogen pz band. Here we present a detailed study of the electronic structure of the nematic superconductors FeSe1−xTex (0 < x < 0.4) using angle-resolved photoemission spectroscopy to understand the role of orbital-dependent band shifts, electronic correlations and the chalcogen band. We assess the changes in the effective masses using a three-band low energy model, and the band renormalization via comparison with DFT band structure calculations. The effective masses decrease for all three-hole bands inside the nematic phase, followed by a strong increase for the band with dxy orbital character. Interestingly, this nearly-flat dxy band becomes more correlated as it shifts towards the Fermi level with increasing Te concentrations and as the second superconducting dome emerges. Our findings suggests that the dxy hole band, which is very sensitive to the chalcogen height, could be involved in promoting an additional pairing channel and increasing the density of states to stabilize the second superconducting dome in FeSe1−xTex. This simultaneous shift of the dxy hole band and enhanced superconductivity is in contrast with FeSe1−xSx.

Quantum spin nematic phase in a square-lattice iridate.

Spin nematic is a magnetic analogue of classical liquid crystals, a fourth state of matter exhibiting characteristics of both liquid and solid1,2. Particularly intriguing is a valence-bond spin nematic3-5, in which spins are quantum entangled to form a multipolar order without breaking time-reversal symmetry, but its unambiguous experimental realization remains elusive. Here we establish a spin nematic phase in the square-lattice iridate Sr2IrO4, which approximately realizes a pseudospin one-half Heisenberg antiferromagnet in the strong spin-orbit coupling limit6-9. Upon cooling, the transition into the spin nematic phase at TC ≈ 263 K is marked by a divergence in the static spin quadrupole susceptibility extracted from our Raman spectra and concomitant emergence of a collective mode associated with the spontaneous breaking of rotational symmetries. The quadrupolar order persists in the antiferromagnetic phase below TN ≈ 230 K and becomes directly observable through its interference with the antiferromagnetic order in resonant X-ray diffraction, which allows us to uniquely determine its spatial structure. Further, we find using resonant inelastic X-ray scattering a complete breakdown of coherent magnon excitations at short-wavelength scales, suggesting a many-body quantum entanglement in the antiferromagnetic state10,11. Taken together, our results reveal a quantum order underlying the Néel antiferromagnet that is widely believed to be intimately connected to the mechanism of high-temperature superconductivity12,13.

The radial hedgehog solution in the Landau–de Gennes theory: Effects of the bulk potentials

We study equilibrium configurations in spherical droplets of nematic liquid crystal with strong radial anchoring, within the Landau–de Gennes theory with a sixth-order bulk potential. The sixth-order potential predicts a bulk biaxial phase for sufficiently low temperatures, which the conventional fourth-order potential cannot predict. We prove the existence of a radial hedgehog solution, which is a uniaxial solution with a single isotropic point defect at the droplet centre, for all temperatures and droplet sizes, and prove that there is a unique radial hedgehog solution for moderately low temperatures, but not deep in the nematic phase. We numerically compute critical points of the Landau–de Gennes free energy with the sixth order bulk potential, with rotational and mirror symmetry, and find at least two competing stable critical points: the biaxial torus and split core solutions, which have biaxial regions around the centre, for low temperatures. The size of the biaxial regions increases with decreasing temperature. We also compare the properties of the radial hedgehog solution with the fourth-order and sixth-order potentials respectively, in terms of the Morse indices as a function of the temperature and droplet radius; the role of the radial hedgehog solution as a transition state in switching processes; and compare the bifurcation plots with temperature, with the fourth- and sixth-order potentials. Overall, the sixth-order potential has a stabilising effect on biaxial critical points and a de-stabilising effect on uniaxial critical points and we discover an altogether novel bulk biaxial critical point of the Landau–de Gennes energy with the sixth-order potential, for which the bulk biaxiality is driven by the sixth-order potential.

Mesomorphism of (E)-4-[(4-propyloxyphenyl)diazenyl]phenyl alkanoates (3OABOOCm)

Several compounds from the group of (E)-4-[(4-propyloxyphenyl)diazenyl]phenyl alkanoates (3OABOOCm, for m = 1 – 19) were synthesized, with the derivatives for m ≥ 8 being reported for the first time. The phase situation was investigated by polarizing optical microscopy, thermo-optical analysis, and differential scanning calorimetry methods. The enantiotropic nematic mesophase was noted for compounds where m = 2 – 13, whereas the monotropic nematic phase was observed for m = 1, 14, and 15. Multiple crystalline phase were noticed in selected derivatives (for m = 1 – 3, 9, 13, and 14). The X-ray powder diffraction confirmed the polymorphism of the crystalline phase for the 3OABOOC2 compound. The trans-cis photoisomerization process is attributed to the presence of the diazenyl (azo) group. Absorption spectra, collected as a function of UV light exposure time, indicated a first-order reaction comprising two components. The determined values of the kinetic constant k were of the order of 10-2s − 1.

Shear-induced flow and dynamics of the nematic phase of Sunset Yellow lyotropic chromonic liquid crystal

ABSTRACT Fundamental understanding of rheological properties of lyotropic chromonic liquid crystals is inadequate compared to their thermotropic counterparts in spite of the growing interest in these materials. Here, we investigate the rheological properties of a lyotropic chromonic nematic liquid crystal (LCLC), prepared by dissolving 32 wt% of Sunset Yellow (SSY) in water. The flow curves (stress-strain rate, σ − γ ˙ ) at different temperatures exhibit three flow regimes R1, R2 and R3, respectively. At room temperature, in R1 ( γ ˙ < γ ˙ cl ) and R3 ( γ ˙ > γ ˙ cu ) the sample exhibits Newtonian flow behaviour ( σ ∝ γ ˙ ), whereas, in R2 ( γ ˙ cl < γ ˙ < γ ˙ cu ), it shows a power-law dependence ( σ ∼ γ ˙ β ). With increasing shear rate the change of stress from R1 to R2 is continuous, whereas the change is discontinuous from R2 to R3. We observe stress fluctuations under steady shear in regime R2 similar to those reported in worm-like micellar systems and in thermotropic twist-bend nematic liquid crystals. The non-monotonic flow behaviour and the stress dynamics are corroborated using in situ rheo-microscopy.

Thermoreversible Gel-Dispersed Liquid Crystals.

A simple model is introduced to describe phase behaviours of binary mixtures of a thermoreversible gel and a low-molecular-weight liquid crystal (LC). We predict novel phase diagrams on the temperature-concentration plane, including sol-gel transition, nematic-isotropic phase transition, and phase separation. At high temperatures, the phase separation between the isotropic sol and gel phases appears. As the temperature decreases, we have the phase separation between nematic sol and isotropic gel phases, in which the nematic domains are dispersed in the isotropic gel phase. We suggest that thermoreversible gelation of reactive molecules mixed with LCs will become one of the new classes of polymer-dispersed liquid crystals.

Effortless Extraction of Structural and Orientational Information from 13C-1H Dipolar Couplings for Thiophene Mesogens.

Five molecular mesogens containing phenyl rings and thiophene are subjected to a detailed 13C NMR investigation. The first mesogen contains only phenyl rings, while the other four have thiophene with substitution at position 2 or 3. Two of these also have a spacer inserted between the thiophene and the rest of the core unit. The mesophase properties evaluated by complementary techniques reveal an enantiotropic nematic phase for all the cases and smectic C as well as Crystal J for a few mesogens. In addition to solution 13C NMR, the samples were studied using 1D and 2D solid-state 13C NMR experiments in the liquid crystalline phase. The chemical shifts and 13C-1H dipolar couplings obtained in the mesophase provided cutting-edge information about the molecular structure and orientation of the thiophene mesogens. Accordingly, dramatic differences in these parameters are noted for the mesogens, and consequently, the identification of 2- and 3-substituted thiophene mesogens is accomplished by a simple visual examination of the 2D spectra. Furthermore, for mesogens with a spacer between thiophene and the rest of the core, 13C chemical shifts and 13C-1H dipolar couplings showed remarkable variation, which was directly reflected in the order parameters. For instance, the order parameter (Szz) of thiophene in 2- and 3-substituted mesogens in which the spacer is absent is ∼0.63 whereas for those with spacer, it is reduced to ∼0.14-0.18. In comparison, the mesogen in which the core unit is made up of phenyl rings alone that is used to benchmark the characteristics of thiophene ordering showed an order parameter of ∼0.85. The study unambiguously demonstrates the supremacy of 13C NMR in extracting the structural and orientational information on mesogens in which thiophene is a constituent of the core unit.

The Ever Elusive, Yet-to-Be-Discovered Twist-Bend Nematic Phase

The second, lower-temperature nematic phase observed in nonlinear dimer liquid crystals has properties originating from nanoscale, polar, intermolecular packing preferences. It fits the description of a new liquid crystal phase discovered by Vanakaras and Photinos, called the polar-twisted nematic. It is unrelated to Meyer’s twist-bend nematic, a meta-structure having a macroscale director topology consistent with Frank–Oseen elastic theory.

Effect of the Structure of Epoxy Monomers and Curing Agents: Toward Making Intrinsically Highly Thermally Conductive and Low-Dielectric Epoxy Resins.

The low intrinsic thermal conduction and high dielectric properties of epoxy resins have significantly limited their applications in electrical and electronic devices with high integration, high frequency, high power, and miniaturization. Herein, a liquid crystalline epoxy (LCE) monomer with a biphenyl mesogenic unit was first synthesized through an efficient one-step reaction. Subsequently, bisphenol AF (BPAF) containing low-polarizable -CF3 groups and 4,4'-diaminodiphenylmethane (DDM) were applied to cure the LCE and commercial diglycidyl ether of bisphenol A-type epoxy (E-51), respectively, to afford four kinds of epoxy resins with various intrinsic thermal conductivity and dielectricity values. Owing to the dual effect of microscopically stacking of mesogens and the contribution of fluorine to the formation of liquid crystallinity, ordered microstructures of the nematic liquid crystal phase were formed within the cross-linking network of LCE as confirmed by polarized optical microscopy and X-ray diffraction. Consequently, phonon scattering was suppressed, and the intrinsic thermal conductivity was improved considerably to 0.38 W/(m·K), nearly twice as high as that of E-51 cured with DDM (0.20 W/(m·K)). Additionally, the ordered microstructure and ultralow polar -CF3 groups within LCE cured with BPAF enabled the epoxy resin to exhibit a remarkably lower and stable dielectric constant (ε) and dielectric loss tangent (tan δ) over both low and high frequencies compared to E-51 cured with DDM. The ε decreased from 3.40 to 2.72 while the tan δ decreased from 0.044 to 0.038 at 10 GHz. This work presents a scalable and facile strategy for breaking the bottleneck of making epoxy resins simultaneously with high inherent thermal conduction and low dielectric performance.

Design and Investigation of a Side-Chain Liquid Crystalline Polysiloxane with a Ntb-Phase-Forming Side Chain

A new mesogenic non-symmetric dimeric monomer with a terminal olefin function, forming a twist bend nematic (Ntb) as well as a nematic (N) phase, was synthesized, using an enhanced synthetic methodology, which avoids isomerization of the terminal double bond in the preparation of the dimer. This monomer was attached to a pentamethyldisiloxane group, resulting in the SmA LC phase behavior of the ensuing material. Linking the monomer to a siloxane main chain resulted in nematic phase behavior. Detailed studies with the Ntb phase forming dimer DTC5C7 show full miscibility of the dimer and the new LC polymer in the LC state, suggesting that the side-chain LC polymer forms a Ntb phase as the low-temperature nematic phase. Copolymerizing the monomer with a cyanobiphenyl-based monomer allows us to tune the glass transition and phase behavior further.