Properties Of Liquid Crystals Research Articles

Phase transition studies of a fluorinated antiferroelectric liquid crystal probed by temperature dependent Raman spectroscopy

Fluorinated liquid crystals (LCs) have emerged as a valuable option for display technologies, rapid switching applications, and photonic devices. Addition of fluorine atoms in the LCs change the electronic distribution within the molecule, introducing required LC properties for various display techniques. In this study, the structural properties of an antiferroelectric LC, (S)-octan-2-yl 2,3-difluoro-4′’-((6-((2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanoyl)oxy) hexyl) oxy)-[1,1′,4′,1′’-terphenyl]-4-carboxylate is investigated using Raman spectroscopy. This LC exhibits a unique orthoconic antiferroelectric arrangement along with chiral smectic C (SmC*) and smectic A (SmA*) phases. Raman spectra were recorded over a temperature range of 20 °C to 130 °C, covering the spectral region of 500–3500 cm−1. Additionally, theoretical Raman spectra at room temperature is simulated using density functional theory (DFT) with the B3LYP functional and 6-31G (d, p) basis set, showing good agreement with experimental results. Through meticulous fitting of the spectral features using Lorentzian profiles, precise values for peak positions, linewidths, and integrated intensities of selected Raman bands are obtained. Changes in Raman spectral parameters at the crystalline-SmCA*, SmCA*-SmC*, SmC*-SmA*, and SmA*-isotropic phase transitions are analyzed in terms of molecular alignment and intra/intermolecular interactions. The Raman spectral results provide a detailed understanding of the molecular and structural behaviour of the liquid crystal as it undergoes various phase transitions with increasing temperature.

Influence of side-methyl substitution position on the phase state and microwave dielectric properties of triphenylacetylene-based liquid crystals.

Liquid crystal materials are well known in display applications, and their unique birefringence and electrical tunability can be utilised in microwave devices. This innovative technology modulates and filters microwave signals, replacing conventional semiconductors for a broad operational frequency band and tunable phase shift. Although isothiocyanatobiphenylacetylene-based liquid crystals exhibit low viscosity and large dielectric anisotropy, their applications in microwave communication are hampered by their broad near-crystalline phase temperature ranges. To address this limitation, this study designed and synthesized six fluorinated biphenylacetylene liquid crystal compounds with various benzene ring side-methyl substitutions (n = 3-5). The molecular structures, liquid crystal phases, and microwave dielectric properties were evaluated. Our findings indicate that compounds with methyl substitution at the Y2 position exhibited reduced melting points, an expanded nematic phase temperature range (ΔT n ≈ 92.3 °C), and an absence of near-crystalline phases. These compounds still maintain high microwave dielectric constants within the 9-30 GHz frequency band (Δε r = 0.9-1.3) and reduced maximum permittivity losses compared to their non-methyl-substituted counterparts, thereby improving the efficiency in the microwave frequency band. In contrast, the Y1 position substitution results in a significantly narrower nematic phase temperature range (approximately 2.6 °C on average) and a substantial decrease in the dielectric constant, with a Δε r reduction of about 0.3 compared to the Y2 substitution. This work shows that the side-methyl substitution can improve the performance of triphenylacetylene-based liquid crystals in microwave communication, providing valuable insight to aid the discovery of novel microwave liquid crystals.

Carbon dots induced homeotropic alignment in a negative dielectric nematic liquid crystal material

Abstract Recently, doping guest materials such as quantum dots (QDs) into liquid crystals (LCs) has been of great interest since their addition substantially enhances the properties of LC and opens new avenues for scientific advancement. Here, we report the induction of homeotropic alignment in cells without alignment layers of the negative dielectric nematic liquid crystal, N-(4-Methoxybenzylidene)-4-butylaniline (MBBA) by doping with carbon dots (CDs ∼2.8 ± 0.72 nm). The CDs-MBBA composites (CDs concentration: 0.002, 0.01, 0.03, 0.1 and 0.3 wt%) were investigated using optical polarising microscopy, electro-optical and dielectric techniques. Polarizing optical micrographs and voltage dependent optical transmission revealed the induced homeotropic alignment for all the composites under investigation. Interestingly, the least concentrated sample, 0.002 wt% exhibited partial homeotropic alignment. However, due to light leakage, the optical transmission value below threshold voltage was relatively higher than the rest of the composites. MBBA is a negative dielectric material, hence the application of a voltage across the cell was able to switch the alignment from a dark to a bright state for all composites. However, above a certain voltage (>threshold voltage), the bright state produced some instabilities. The value of dielectric permittivity was observed to decrease with increasing concentration, confirming the effect of CDs in producing homeotropic alignment in MBBA. Measurements as a function of temperature were conducted to examine the thermal stability of the induced alignment. The alignment was found to be stable throughout the nematic phase of MBBA. The induction of such alignment without conventional alignment (i.e., rubbing of polyimides) technique can be helpful in addressing the evolving display demands by making liquid crystal displays (LCDs) and other display devices cost effective.

Synthesis and liquid crystal properties of a new class of calamitic mesogens based on twin 1,3,4-thiadiazole derivatives with imine linkage

The synthesis and characterization of two distinct novel series of compounds, [II]n and [V]n , containing 1,3,4-thiadiazole units, were studied in this work. The central core of the first series is phenyl, whereas the central core of the second series is OCH2CH2O. FTIR,1HNMR,13CNMR, and mass spectroscopy are used to characterize the materials used in this investigation. Liquid crystalline properties were confirmed by the use of differential scanning calorimeter (DSC) and hot-stage polarizing optical microscopy (POM). While other compounds showed no liquid crystalline behavior, the compounds [II]3 –[II]6 , [V]1 and [V]n showed enantiotropic nematic and smectic phases.

Dielectric and electrical properties of liquid crystals doped with ferroelectric nanoparticles

ABSTRACT The present work examines the impact of incorporating ferroelectric Ba0.85Sr0.15TiO3 nanoparticles (NPs) on the thermodynamic, dielectric, electrical, ionic, and electro-optical properties of 4-cyano-4’-octylbiphenyl (8CB) as Liquid Crystal (LC). The introduction of ferroelectric NPs results in a notable elevation of the nematic-isotropic phase transition temperature, which is consistent with theoretical models. Impedance spectroscopy was employed to investigate bulk and interfacial phenomena, revealing a low-frequency relaxation mode attributed to space charge polarisation. In comparison to the pure LC, the dielectric anisotropy and the DC conductivity were found to be increased in the doped samples. Furthermore, the reduction in the concentration of ions on the surface, their diffusion constant, and their mobility, coupled with a decrease in the threshold voltage, simultaneously indicate the trapping of ions by the ferroelectric NPs. The screening effect renders dispersed ferroelectric NPs an optimal solution for addressing the issue of ionic contamination and eliminating its deleterious effects.

A Novel High Proton Conductivity Hydrogen Bond Self-assembly Proton Exchange Membrane with Liquid Crystal Properties

A Novel High Proton Conductivity Hydrogen Bond Self-assembly Proton Exchange Membrane with Liquid Crystal Properties

Cold and Liquid Crystal Properties of Square-Planar Copper(II) Versus Nickel(II)- Iminophenolate/Naphthalen-2-Olate Schiff Base Complexes.

Reaction of the phenolate or naphthalen-2-olate based Schiff base ligands, (E)-1-((2-ethylphenylimino)methyl)phenol (HL1) or (E)-1-((2-ethylphenylimino)methyl)naphthalen-2-ol (HL2) with nickel(II) and copper(II) acetate provides the complexes bis[(E)-1-((2-ethylphenylimino)methyl)phenolato-ĸ2N,O]Ni/Cu(II), [Ni(L1)2] (1) and [Cu(L1)2] (2), or bis[(E)-1-((2-ethylphenylimino)methyl)naphthalen-2-olato-ĸ2N,O]Ni/Cu(II), [Ni(L2)2] (3) and [Cu(L2)2] (4), respectively. Single crystal X-ray structure determinations for 1, 3 and 4 reveal N2,O2-metal coordination of two chelating Schiff base ligands in a square-planar geometry. Powder X-ray diffractograms confirm the phase purity of the bulk microcrystalline samples. Thermal analyses by differential scanning calorimetry (DSC) and polarized light microscopic (PLM) indicate the copper(II) complexes to exhibit cold crystal (2) and liquid crystal (4) property. Cyclic voltammograms suggest an irreversible electrochemical process with two one electron charge transfer processes in N,N-dimethylformamide. Variable temperature magnetic measurements at the solid-state prove the diamagnetic nature of the low-spin Ni2+ centres in 1 or 3, as expected from the square-planar coordination geometry with rather strong ligands. The complexes expose medium level of antioxidant activity in methanol. Optimized geometry and excited state property by DFT/TD-DFT correspond well to the experimental results of the electronic and molecular structure at the ground state.

Spin‐Crossover and Liquid Crystal Property in Fe(II) Complexes: Impact of Alkyl Chain Lengths

AbstractMaterials that combine spin‐crossover (SCO) and liquid crystal (LC) behavior have gained significant attention due to their potential applications in technological devices, attributed to their easy processability. Herein, we report three neutral heteroleptic Fe(II) complexes: [Fe(dpa‐C4)2(NCS)2] (1), [Fe(dpa‐C6)2(NCS)2] (2), and [Fe(dpa‐C16)2(NCS)2] (3) (dpa‐Cn=N‐alkyl‐N‐(pyridin‐2‐yl)pyridin‐2‐amine; n=4, 6 and 16), which exhibit thermal‐induced spin transition behavior. The transition profiles and temperatures are effectively modulated by the length of the alkyl chains. Longer alkyl chains result in gradual and higher T1/2 values, while the shorter chains lead to abrupt SCO with lower T1/2 (i. e. T1/2=259 K (3) >237 K (2) >211 K (1)). Crystallographic studies reveal the impact of hydrophobic and hydrophilic packing in the crystal lattice, contributing to cooperativity and thereby affecting the SCO behavior. Complex 3 with long alkyl chain substitution, displayed non‐synchronized SCO‐LC behavior due to the thermal motion of the alkyl chains.

Microfluidic Exploitation of Liquid Crystal Properties of Boron Nitride Nanotubes and Enhancing Neutron Shielding with Aligned Structure

Boron nitride nanotubes (BNNTs) are cylindrical nanostructures characterized by alternating boron and nitrogen atoms. Unlike carbon nanotubes (CNT), BNNTs are electrically insulating and exhibit high thermal stability and neutron shielding capabilities. Their unique tubular structure enables the formation of 1D arrays, which can achieve a nematic liquid crystal phase, ideal for fabricating high‐density structures. However, the widespread application of BNNTs has been hindered by challenges in purifying and dispersing high‐purity BNNTs. This study aims to exploit the liquid crystal properties of BNNTs by generating high‐purity BNNT dispersions through a series of dispersion and purification processes. Furthermore, this study utilizes microfluidics technology to encapsulate the BNNT dispersions. Using this approach, the transition of liquid crystal phases in relation to BNNT concentration is efficiently examined. This process results in the production of high‐density BNNT films characterized by pronounced anisotropy, which in turn provides significant thermal neutron shielding effects.

Effect of alkyl chains on the structural and optical properties of nH6BiN orthoconic antiferroelectric liquid crystals: Insights from DFT calculations

This research presents a detailed computational study of a homologous series of orthoconic antiferroelectric liquid crystalline compounds, nH6BiN (where n = 1–6), employing Density Functional Theory (DFT) with the B3LYP functional and 6-311G(d,p) basis set. We optimized the molecular geometry and used it as an input file for analyzing thermodynamic properties, vibrational spectroscopy, and evaluating non-linear optical (NLO) properties to investigate the impact of terminal chain length on these compounds. The electronic structure analysis, including HOMO-LUMO gap and reactivity parameters, indicated consistent electronic properties across the series. Raman spectroscopy confirmed structural regularity, with characteristic vibrational modes. Notably, non-linear optical properties enhanced with chain length, as evidenced by increasing dipole moments, polarizabilities, and hyperpolarizabilities. The results highlight the influence of terminal chain length on the structural, electronic, and optical properties of the nH6BiN compounds, providing valuable insights for material design. This comprehensive study provides insights into the influence of terminal chain length on the molecular properties of the nH6BiN series, offering a foundation for their potential application in advanced material science.

Aryl/fluoroaryl-substituted triphenylene discotic liquid crystals: Synthesis, mesomorphism, and photophysical properties

Fluorine aromatic hydrocarbons are ubiquitous optoelectronic functional materials and their efficient synthetic methods are still the subject of rapid, ongoing development. Here, several aryl- and fluoroaryl-substituted triphenylenes (Ar-TP/FAr-TP) were synthesized via either Suzuki-Miyaura cross-coupling or aromatic nucleophilic substitution (SNAr) of perfluoroarenes, respectively, starting indifferently from 2-bromo-3,6,7,10,11-pentakis(hexyloxy)triphenylene (Br-TP). These compounds possess very high thermal stability with initial decomposition temperature over 300 °C, as measured by thermal gravimetric analysis (TGA). Differential scanning calorimetry (DSC), polarized optical microscopy (POM), and small/wide angle X-ray scattering (S/WAXS) revealed that they all self-organize into hexagonal columnar (Colhex) mesophase over broad temperature ranges, occurring at room temperature for some of them, with higher stability than the archetypical 2,3,6,7,10,11-hexakis(hexyloxy)triphenylene parent compound. Under the combined influence of the conjugated π-system and core-side arm distortion, the clearing temperatures and mesophase ranges increase from phenyl- (P-TP), naphthyl- (N-TP), to biphenyl-triphenylene (BP-TP). The number of fluorine atoms on the side fluoroaryl group also impacts the columnar mesomorphism: the more fluorine atoms, the higher the clearing temperatures and the wider the Colhex phase ranges, concomitantly with increasing arene-fluorarene intermolecular interactions. In addition, these compounds show blue-violet photoluminescence in solution: the largest fluorescent absolute quantum yield is measured for BP-TP (45 %), while the smallest is for 7FN-TP (10 %). Perfluoroaryls tend to lower the LUMO, which results in fluorescence red-shift. The arene-perfluoroarene polar-π interactions improve the physical properties of these FAr-TP discotic liquid crystals.

Widely tunable reflection by a hybrid ion-doped positive-negative chiral nematic liquid crystal under an electric field.

In this study, a new methodology, in which the cation and chiral agent are doped in positive and negative nematic liquid crystal mixture to form cation-doped positive-negative chiral nematic liquid crystals (PN-CNLCs), is proposed. These PN-CNLCs are capable of achieving a wide wavelength tuning range close to 90 nm under the action of a high-frequency electric field. The dielectric interaction between these two liquid crystals with different dielectric anisotropies in the electric field allows for the effective change of the pitch of the CLCs. We discovered the tilting of the pitch in the PN-CNLCs by a series of well-designed validation experiments. The experimental results prove the symmetrical helix is formed along the alignment direction in PN-CNLCs. Furthermore, the experiments demonstrated that an increase in voltage does not directly affect the pitch, but it increases the tilt angle of the helix axis with respect to the normal of the LC cell. This study offers, to our knowledge, a novel perspective on the tuning performance of CLCs under electric field conditions, by integrating the properties of positive and negative liquid crystals. This finding not only contributes to the understanding of the electric field response mechanism of CLCs but also provides new avenues for the application of CLCs in fields such as wavelength tuning.

A novel multifunctional naphthalene triazole columnar liquid crystal: synthesis, self-assembly and application in silicon solar cells

Herein, click reaction was used as a crucial step to effectively synthesize a new multifunctional naphthalene triazole columnar liquid crystal ICm/n. The properties of liquid crystal and gel in ICm/n were investigated using POM, DSC, XRD and SEM. ICm/n can self-assemble into square columnar liquid crystals in their pure state and form organogels in N,N-dimethylformamide (DMF). In addition, ICm/n can be used as a Fe3+ chemosensor. Interestingly, the addition of lithium salts has a significant impact on the self-assembly, molecular dynamics and ionic conductivity of the compounds, thus potentially providing nanostructured LC electrolytes with continuous substrate ionic conductivity. Additionally, the use of ICm/n as a dopant in the poly (3,4-ethylenedioxythiophene): polystyrene (PEDOT: PSS) hole injection layer greatly enhanced the photoelectric conversion efficiency (PCE) of Si/PEDOT: PSS heterojunction solar cells, boosting it from 2.08 % to 8.10 %. The current work offers a novel method for creating liquid crystal (LC) materials with several uses for naphthalene triazoles.

Effect of Guest Particles on the Functional Dielectric Properties of Materials for Display Application

AbstractIn this study the dielectric properties are experimentally studied and also analyzed the influence of guest particles on the functional properties of various liquid crystals. The polar and elastic energy of the nanoparticles is found to affect the functional energy of pure suspension. In addition to this, the functional dielectric anisotropy of the dispersed system takes modified form. In this study experiments are performed on various materials to find dielectric anisotropy and also found in good agreement with theoretical explanation.

Cholesteric Liquid Crystal Mirror-Based Smart Window Controlled with Ambient Temperature

In this paper, the authors demonstrate a small prototype of a smart window based on the thermo-optical properties of cholesterol liquid crystals. Due to its polymer-free design, the manufactured smart window is transparent and can reflect certain portions of visible or infrared light without requiring an external power source, and thus is easier to install and operate. The proposed smart window technology based on a cholesteric liquid crystal mirror will reduce energy consumption costs by reflecting excess sunlight and heat transfer, increasing comfort for residents of buildings and structures.

Electrically Tunable Chiral Ferroelectric Nematic Liquid Crystal Reflectors

AbstractManipulating light is an important area of optical research and development. To that end, tunable dichroic devices in which the reflectivity at differing wavelengths can be adjusted, are particularly valuable. This work is motivated by recent studies of the optical properties of chiral ferroelectric nematic liquid crystals (FNLCs). Here electro‐optical studies are presented on two room temperature, FNLC materials that demonstrate electrically tunable reflectivity when subject to a field below 0.2 V µm−1. Moreover, under appropriate conditions, the reflectivity can also be electrically (and reversibly) tuned (without change of color) from 0% to 40%. Reversible, low voltage tunable mirrors, having miniscule power consumption and operable around ambient temperature are expected to be useful in diverse applications ranging from energy‐saving, smart windows to virtual reality interfaces.

Supramolecular Arrangement and Conformational and Dynamic Properties of Chiral Smectic Liquid Crystals Obtained through Nuclear Magnetic Resonance: A Brief Review

Ferroelectric and antiferroelectric smectic liquid crystalline (LC) phases are still at the center of investigations and interests for both their fundamental properties and variety of technological applications. This review aims to report the main contributions based on different nuclear magnetic resonance (NMR) techniques to the study of chiral liquid crystalline calamitic mesogens forming smectic phases, such as the SmA, the SmC* (ferroelectric), and the SmC*A (antiferroelectric) phases. 2H NMR and 13C NMR techniques and their combination were of help in clarifying the local orientational properties (i.e., the molecular and fragments’ main orientational order parameters) at the transition between the SmA and the SmC* phases, and in the particular case of de Vries liquid crystals, NMR studies gave important clues regarding the actual models describing the molecular arrangement in these two phases formed by de Vries LCs. Moreover, this review describes how the combination of 2H NMR relaxation times’ analysis, 1H NMR relaxometry, and 1H NMR diffusometry was successfully applied to the study of chiral smectogens forming the SmC* and SmC*A phases, with the determination of relevant parameters describing both rotational molecular and internal motions, collective dynamics, and translational self-diffusion motions. Several cases will be reported concerning NMR investigations of chiral ferroelectric and antiferroelectric phases, underlining the great potential of combined NMR approaches to the study of supramolecular, conformational, and dynamic properties of liquid crystals.

Enhanced electro-optical properties of polymer dispersed liquid crystals doped with functional nanofibers for applications of efficient smart windows and advanced anti-counterfeiting

The development of polymer-dispersed liquid crystal (PDLC) capable of infrared smart tuning and displaying distinct information under ultraviolet, visible, and infrared light presents significant challenges. These challenges include the tuning of electro-optical properties and IR reflectivity, the preparation of complex patterns, and the display of different display states under various stimuli. In this work, nanofibers doped with alumina-zinc oxide nanoparticles (AZO NPs) and loaded with cesium tungstate nanoparticles (Cs0.33WO3 NPs) into PDLC not only enhanced their electro-optical properties but also added infrared shielding. Temperature regulation tests demonstrate that PDLC films can intelligently modulate infrared light reflection, offering superior shading and temperature regulation capabilities. PDLC smart windows integrated with nanofibers achieve a temperature coordination function, maintaining a temperature differential of 12.1 °C compared to standard PDLC. This significant enhancement underscores their potential for applications in thermally regulated smart windows. In addition, a full-wavelength anti-counterfeiting mode for PDLC was developed using a screen-printing strategy to display different information under various wavelengths of light. Noteworthily, the anti-counterfeiting system exhibits a bright fluorescent pattern under UV light, a scattering pattern under visible light, and an infrared-modulated pattern when viewed with an infrared detector. Furthermore, an advanced dynamic anti-counterfeiting mode with time response was created using nanofibers loaded with different concentrations of Cs0.33WO3 NPs. This advanced anti-counterfeiting material can be used as multimodal and dynamic anti-counterfeiting label, which greatly facilitates the development of novel anti-counterfeiting and optical sensing materials.

Magnetically induced tunable exceptional and Dirac points

The photonic properties of cholesteric liquid crystals (CLCs) in an external magnetic field parallel to the helix axis are theoretically investigated for the first time in the short-wavelength band of the spectrum, where exceptional points (EPs) are found. It was shown that at the EP the real parts of two of four wave numbers touch each other or intersect at the absence of the dielectric anisotropy, and their imaginary parts intersect. At the EP the reflection, transmission and absorption show the same magnitudes for two eigenmodes of CLC layer. At anisotropic absorption near the EP there appear points where the magnetically induced transmittance/absorption are observed. The tunability of the EP was shown, i.e. we can change its wavelength by changing the magnitude of the external magnetic field. It was demonstrated the resonant enhancement of the chirality near the EP. Then it was shown that near the EP the two eigenmodes of CLC layer become strongly non-orthogonal.

Synergistic effects of anionic surfactant doping on dielectric and electro-optical properties of nematic liquid crystals by cyano-ionic interactions

Modern research has long focused on controlling and optimizing the dielectric, electro-optical and optical attributes of liquid crystals (LCs) to increase their technological value. Numerous approaches have been investigated for this reason in an effort to overcome various issues such as high response time, high driving voltage requirements, low dielectric anisotropy and limited operating temperature range, etc. The strategy utilizing binary/multicomponent systems is the most investigated and seems to have the most potential out of all the other techniques. In keeping with the same subject, the influence of anionic surfactant on the dielectric, electro-optical, and optical properties of nematic LC (NLC) has been examined. Precisely, dodecane-1-sulfonic acid sodium salt (SDS) which is an anionic surfactant was dispersed in a room temperature NLC E7 at various concentrations. Our findings reveal a significant alteration in the electro-optical behavior resulting from the introduction of an anionic surfactant, extending well beyond the instance of electrode polarization, albeit with a detrimental impact on performance within the low-frequency range as a result of increased ionic contribution. The main findings of this study include a 17.5%% increase in dielectric anisotropy, an appreciable reduction of about 30%% in threshold voltage and rotational viscosity, and approximately 64% reduction in response time in the host NLC due to the addition of anionic salt in it. A significant photoluminescence quenching of about 64%% is observed after dispersion of 3.0% by weight anionic surfactant in E7. These findings offer potential pathways for the development of future technologies in various domains, including photonic devices, biological imaging, light-emitting diodes (LEDs), and luminescent markers.