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Keywords = smectic liquid crystal

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23 pages, 5986 KiB  
Article
Partially Disordered Crystal Phases and Glassy Smectic Phases in Liquid Crystal Mixtures
by Aleksandra Deptuch, Anna Drzewicz, Magdalena Urbańska and Ewa Juszyńska-Gałązka
Materials 2025, 18(13), 3085; https://doi.org/10.3390/ma18133085 - 29 Jun 2025
Viewed by 293
Abstract
Three liquid crystalline mixtures were investigated, consisting of compounds abbreviated as MHPOBC and 3F5FPhF6 with molar ratios 0.9:0.1 (MIX5FF6-1), 0.75:0.25 (MIX5FF6-2), and 0.5:0.5 (MIX5FF6-3). The presence of the smectic A*, smectic C*, and smectic CA* phases was observed in all mixtures. [...] Read more.
Three liquid crystalline mixtures were investigated, consisting of compounds abbreviated as MHPOBC and 3F5FPhF6 with molar ratios 0.9:0.1 (MIX5FF6-1), 0.75:0.25 (MIX5FF6-2), and 0.5:0.5 (MIX5FF6-3). The presence of the smectic A*, smectic C*, and smectic CA* phases was observed in all mixtures. The hexatic smectic XA* phase, present in pure MHPOBC, disappeared quickly with an increasing admixture of 3F5FPhF6. Vitrification of smectic CA* was observed for the equimolar mixture, with the glass transition temperature and fragility index comparable to the pure glassforming 3F5FPhF6 component. Partial crystallization to conformationally or orientationally disordered crystal phases was observed on cooling in two mixtures with a smaller fraction of 3F5FPhF6. Broadband dielectric spectroscopy was applied to study the relaxation times in smectic and crystal phases. Vogel–Fulcher–Tammann, Mauro–Yue–Ellison–Gupta–Allan, and critical-like models were applied for analysis of the α-relaxation time in supercooled smectic XA* and smectic CA* phases. Full article
(This article belongs to the Special Issue Structural and Physical Properties of Liquid Crystals)
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18 pages, 2433 KiB  
Article
Development of 2,1,3-Benzothiadiazole-Based Room-Temperature Fluorescent Nematic Liquid Crystals
by Muhammad Suhail bin Uzair, Yoshimichi Shimomura, Takuya Tanaka, Takashi Kajitani and Gen-ichi Konishi
Molecules 2025, 30(11), 2438; https://doi.org/10.3390/molecules30112438 - 2 Jun 2025
Viewed by 1316
Abstract
Fluorescent liquid crystals (LCs) have attracted considerable interest owing to their unique combination of fluidity, anisotropy, and intrinsic emission. However, most reported fluorescent LCs exhibit high phase transition temperatures and/or smectic phases, limiting their practical applications. To address this, we designed and synthesized [...] Read more.
Fluorescent liquid crystals (LCs) have attracted considerable interest owing to their unique combination of fluidity, anisotropy, and intrinsic emission. However, most reported fluorescent LCs exhibit high phase transition temperatures and/or smectic phases, limiting their practical applications. To address this, we designed and synthesized a series of 2,1,3-benzothiadiazole (BTD)-based fluorescent nematic liquid crystals incorporating donor (D) or acceptor (A) groups to form D–A–D or D–A–A structures. Most of the synthesized derivatives exhibited supercooled nematic phases at room temperature. They composed various functional groups, such as secondary alkylamine, branched alkyl chain, and trifluoroacetyl groups, which are rarely used in calamitic nematic LCs. Notably, dimethylamine- and carbonyl-substituted derivatives exhibited relatively high fluorescence quantum yields (Φfl) in both solid and mesophase states, demonstrating their potential as efficient fluorescent materials. Our findings underscore the versatility of BTD-based mesogenic skeletons for designing room-temperature fluorescent nematic LCs with various functional groups. These materials offer promising opportunities for next-generation display technologies, optical sensors, and photonic applications. Full article
(This article belongs to the Special Issue Photochemistry in Asia)
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15 pages, 3855 KiB  
Article
Thermocapillary Flow in Fluid Smectic Bubbles in Microgravity
by Eric Minor, Ravin Chowdhury, Cheol S. Park, Joseph E. Maclennan and Noel A. Clark
Crystals 2025, 15(5), 416; https://doi.org/10.3390/cryst15050416 - 29 Apr 2025
Viewed by 450
Abstract
Interfaces between two fluids exhibit an excess free-energy cost per unit area that is manifested as surface tension. This equilibrium property generally depends on temperature, which enables the phenomenon of thermocapillary flow, wherein application of a temperature gradient having a component parallel to [...] Read more.
Interfaces between two fluids exhibit an excess free-energy cost per unit area that is manifested as surface tension. This equilibrium property generally depends on temperature, which enables the phenomenon of thermocapillary flow, wherein application of a temperature gradient having a component parallel to the surface generates a net in-plane effective body force on the fluid and thereby causes flow. Here, we study the thermocapillary flow in fluid smectic liquid crystal films freely suspended in air and stabilized in thickness by the smectic layering. If such films are a single layer (~3 nm) or a few layers thick, they have the largest surface to volume ratio of any fluid preparation, making them particularly interesting in the context of thermocapillary flow, which is two-dimensional (2D) in the film plane. Five-layer thick films in the form of spherical bubbles were subjected to a north–south temperature gradient field along a polar axis, with flow fields mapped using inclusions on the film surface as tracers, where the inclusions were “islands”, small circular stacks of extra layers. These experiments were carried out on the International Space Station to avoid interference from thermal convention of the air. The flow field as a function of latitude on the bubble can be successfully modeled using Navier–Stokes hydrodynamics, modified to include permeative flow out of the background fluid into the islands. Full article
(This article belongs to the Section Liquid Crystals)
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15 pages, 9424 KiB  
Article
Liquid Crystalline Structures Formed by Sphere–Rod Amphiphilic Molecules in Solvents
by Nilanthi P. Haputhanthrige, Yifan Zhou, Jingfan Wei, Min Gao, Tianbo Liu and Oleg D. Lavrentovich
Crystals 2025, 15(2), 177; https://doi.org/10.3390/cryst15020177 - 13 Feb 2025
Cited by 1 | Viewed by 968
Abstract
Self-assembly of amphiphilic molecules is an important phenomenon attracting a broad range of research. In this work, we study the self-assembly of KTOF4 sphere–rod amphiphilic molecules in mixed water–dioxane solvents. The molecules are of a T-shaped geometry, comprised of a hydrophilic spherical [...] Read more.
Self-assembly of amphiphilic molecules is an important phenomenon attracting a broad range of research. In this work, we study the self-assembly of KTOF4 sphere–rod amphiphilic molecules in mixed water–dioxane solvents. The molecules are of a T-shaped geometry, comprised of a hydrophilic spherical Keggin-type cluster attached by a flexible bridge to the center of a hydrophobic rod-like oligodialkylfluorene (OF), which consists of four OF units. Transmission electron microscopy (TEM) uncovers self-assembled spherical structures of KTOF4 in dilute solutions. These spheres are filled with smectic-like layers of KTOF4 separated by layers of the solution. There are two types of layer packings: (i) concentric spheres and (ii) flat layers. The concentric spheres form when the dioxane volume fraction in the solution is 35–50 vol%. The flat layers are formed when the dioxane volume fraction is either below (20 and 30 vol%.) or above (55 and 60 vol%.) the indicated range. The layered structures show no in-plane orientational order and thus resemble thermotropic smectic A liquid crystals and their lyotropic analogs. The layered packings reveal edge and screw dislocations. Evaporation of the solvent produces a bulk birefringent liquid crystal phase with textures resembling the ones of uniaxial nematic liquid crystals. These findings demonstrate that sphere–rod molecules produce a variety of self-assembled structures that are controlled by the solvent properties. Full article
(This article belongs to the Special Issue Liquid Crystal Research and Novel Applications in the 21st Century)
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9 pages, 3220 KiB  
Communication
Evolution of Focal Conic Domains in SmA-N Phase Transition
by Vincent Plée, Jordan Lacam, Gianni Pascoli and Claire Meyer
Materials 2025, 18(3), 711; https://doi.org/10.3390/ma18030711 - 6 Feb 2025
Viewed by 689
Abstract
Focal conics are nice geometric structures of liquid crystal phases which present periodicity such as smectic phase, cholesteric phase, etc. Here, we focus on focal conic domains (FCD) in smectic A liquid crystal. During a phase transition from smectic A to nematic, these [...] Read more.
Focal conics are nice geometric structures of liquid crystal phases which present periodicity such as smectic phase, cholesteric phase, etc. Here, we focus on focal conic domains (FCD) in smectic A liquid crystal. During a phase transition from smectic A to nematic, these FCDs evolve as the eccentricity increases until they completely disappear. Here, we present experimental observations of this phenomenon, along with a modeling approach that allows for an interestingly precise description of the phenomenon, revealing, in particular, a coefficient that seems to exhibit the behavior of a critical exponent. Full article
(This article belongs to the Section Soft Matter)
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21 pages, 12910 KiB  
Article
Crystallization Kinetics of an Equimolar Liquid Crystalline Mixture and Its Components
by Aleksandra Deptuch, Anna Paliga, Anna Drzewicz, Marcin Piwowarczyk, Magdalena Urbańska and Ewa Juszyńska-Gałązka
Appl. Sci. 2024, 14(24), 11701; https://doi.org/10.3390/app142411701 - 15 Dec 2024
Cited by 1 | Viewed by 1043
Abstract
This new equimolar mixture comprises the liquid crystalline compounds MHPOBC and partially fluorinated 3F2HPhF6. The phase sequence of the mixture was determined by differential scanning calorimetry, polarizing optical microscopy, X-ray diffraction, and broadband dielectric spectroscopy. The enantiotropic smectic A*, C*, and CA [...] Read more.
This new equimolar mixture comprises the liquid crystalline compounds MHPOBC and partially fluorinated 3F2HPhF6. The phase sequence of the mixture was determined by differential scanning calorimetry, polarizing optical microscopy, X-ray diffraction, and broadband dielectric spectroscopy. The enantiotropic smectic A*, C*, and CA* phases were observed for the mixture. Only partial crystallization of the mixture was observed during cooling at 2–40 K/min, and the remaining smectic CA* phase underwent vitrification. In contrast, the crystallization of the pure components was complete or almost complete for the same range of cooling rates. The kinetics of the non-isothermal and isothermal crystallization of the mixture and its pure components were investigated by differential scanning calorimetry. The non-isothermal data were analyzed by the isoconversional method, while the isothermal data were analyzed using the Avrami model. As is typical, the nucleation-controlled crystallization kinetics were observed. Full article
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17 pages, 4795 KiB  
Article
Aggregation-Induced Emission-Active Cyanostilbene-Based Liquid Crystals: Self-Assembly, Photophysical Property, and Multiresponsive Behavior
by Bian Li, Junde Zhang, Juan Wang and Xiaofang Chen
Molecules 2024, 29(23), 5811; https://doi.org/10.3390/molecules29235811 - 9 Dec 2024
Cited by 2 | Viewed by 1281
Abstract
Cyanostilbene (CS)-related conjugated groups can be considered as dual functional groups of AIEgen and mesogen to construct photoluminescent liquid crystals, and it is essential to study the relationship between their molecular structures and compound properties systematically. In this paper, we designed and synthesized [...] Read more.
Cyanostilbene (CS)-related conjugated groups can be considered as dual functional groups of AIEgen and mesogen to construct photoluminescent liquid crystals, and it is essential to study the relationship between their molecular structures and compound properties systematically. In this paper, we designed and synthesized linear and bent-shaped CS derivatives containing ester- and amide-connecting groups and different substituted numbers of alkoxy tails. Their phase behaviors and photophysical properties were investigated in depth. The bent-shaped compounds with the mono-substituted alkoxy tail exhibit a smectic C structure, and those containing two or three alkoxy tails possess a hexagonal columnar phase structure. The compounds exhibit aggregation-induced emission (AIE) properties in tetrahydrofuran (THF)/water mixtures. When the water fraction increases to a certain threshold, a dramatic increase in emission intensity and a red-shift in the fluorescence emission peak are detected. The emission peaks of the ester-type compounds in solid states are around 480 nm, and those of the amide-type compounds are extended to 590 nm, exhibiting versatile luminescent colors. Moreover, thermochromic and photochromic fluorescence-responsive properties are witnessed in these CS derivatives. This work provides a new strategy for the design and synthesis of fluorescent liquid crystalline materials with multiple response properties. Full article
(This article belongs to the Special Issue Polymeric Liquid Crystals and Applications, 2nd Edition)
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13 pages, 3036 KiB  
Article
Asymmetric Imidazolium-Based Ionic Liquid Crystal with Enhanced Ionic Conductivity in Low-Temperature Smectic Phases
by Yuna Kim, Alagan Jeevika, Tomoya Suwa, Kazuya Kubo and Ken-ichi Iimura
Crystals 2024, 14(12), 1053; https://doi.org/10.3390/cryst14121053 - 3 Dec 2024
Cited by 1 | Viewed by 1367
Abstract
We report the synthesis and characterization of a novel asymmetric imidazolium-based ionic liquid crystal (ILC) dimer exhibiting stable smectic phases over a wide temperature range, including room temperature. This unique molecular structure, combining two distinct mesogenic cores, reduces packing density, which enhances ion [...] Read more.
We report the synthesis and characterization of a novel asymmetric imidazolium-based ionic liquid crystal (ILC) dimer exhibiting stable smectic phases over a wide temperature range, including room temperature. This unique molecular structure, combining two distinct mesogenic cores, reduces packing density, which enhances ion mobility and achieves high ionic conductivity in the smectic phase (0.1 mS cm−1 at 40 °C). Electrochemical impedance spectroscopy (EIS) confirmed improved ionic conductivity at lower temperatures, along with a stable electrochemical window of ±3 V. Application as a solid-state electrolyte in an electrochromic device demonstrated effective switching behavior and reversible redox cycles. These findings suggest that this asymmetric imidazolium-based ILC is a viable candidate for advanced electrochemical applications due to its structural stability and anisotropic ionic pathways. Full article
(This article belongs to the Special Issue Liquid Crystal Materials and Devices)
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13 pages, 2973 KiB  
Article
Liquid Crystal Ordering in Densely Packed Colloidal Suspensions of Highly Anisotropic Monolayer Nanosheets
by Yue Shi, Min Shuai, Yongqiang Shen, Dong Chen, Joseph E. Maclennan, Zhengdong Cheng and Noel A. Clark
Crystals 2024, 14(11), 963; https://doi.org/10.3390/cryst14110963 - 6 Nov 2024
Viewed by 1071
Abstract
Monolayer nanosheets of zirconium phosphate in aqueous suspension exhibit short-range repulsion and long-range attraction, producing, at overall volume fractions larger than about half a percent, phase separation into higher-concentration liquid crystal and lower-concentration isotropic regions. At high concentrations, this phase separation takes the [...] Read more.
Monolayer nanosheets of zirconium phosphate in aqueous suspension exhibit short-range repulsion and long-range attraction, producing, at overall volume fractions larger than about half a percent, phase separation into higher-concentration liquid crystal and lower-concentration isotropic regions. At high concentrations, this phase separation takes the form of an emulsion of condensed, liquid-crystalline droplets, which anneal to form lens-shaped tactoids. These tactoids provide an opportunity to study the liquid crystal ordering of inorganic nanosheets in the limit of large shape anisotropy (diameter/thickness~400) and high packing fraction (volume fraction 70%). The internal liquid crystal structure of the tactoids remains nematic even under conditions that would usually favor ordering into lamellar smectics. Local lamellar ordering is suggested by short-range, smectic-like layer correlations, but a full transition into a smectic phase appears to be inhibited by the nanosheet edges, which act as a perturbative population of dislocation loops in the system of layers. Under conditions of thermal equilibrium, the nanoplates organize positionally to enable bend deformation of the director, a hallmark of the nematic phase and its principal distinction from the smectic, where bend must be expelled. Full article
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9 pages, 5882 KiB  
Article
Topological Defect Evolutions Guided by Varying the Initial Azimuthal Orientation
by Yanchun Shen, Jinbing Wu, Jingge Wang, Saibo Wu and Wei Hu
Appl. Sci. 2024, 14(21), 9869; https://doi.org/10.3390/app14219869 - 29 Oct 2024
Viewed by 1156
Abstract
Topological defects are a key concern in numerous branches of physics. It is meaningful to exploit the topological defect evolutions during the phase transitions of condensed matter. Here, via varying the initial azimuthal orientation of the square alignment lattice in a hybrid cell, [...] Read more.
Topological defects are a key concern in numerous branches of physics. It is meaningful to exploit the topological defect evolutions during the phase transitions of condensed matter. Here, via varying the initial azimuthal orientation of the square alignment lattice in a hybrid cell, the topological defect evolution of liquid crystal during the nematic (N)–smectic A (SmA) phase transition is investigated. The director fields surrounding ±1 point defects are manipulated by predesigning the initial azimuthal orientation. When further cooled to the SmA phase, spiral toric focal conic domain (TFCD) arrays are formed as a result of twisted deformation suppression and unique symmetry breaking after the phase transition. The variation in the azimuthal orientation causes the TFCDs to degenerate from infinite rotational symmetry to quadruple rotational symmetry, thus releasing new textures for the SmA phase. Landau–de Gennes numerical modeling is adopted to reproduce the director distributions in the N phase and reveal the evolution of the topological defects. This work enriches the knowledge on the self-organization of soft matter, enhances the capability for the manipulations of topological defects, and may inspire new intriguing applications. Full article
(This article belongs to the Section Applied Physics General)
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10 pages, 2170 KiB  
Article
Nanostructured Polymer-Dispersed Liquid Crystals Using a Ferroelectric Smectic A Liquid Crystal
by Masaki Yamaguchi, Hiroyuki Matsukizono, Yasushi Okumura and Hirotsugu Kikuchi
Molecules 2024, 29(20), 4837; https://doi.org/10.3390/molecules29204837 - 12 Oct 2024
Cited by 3 | Viewed by 1811
Abstract
Nanostructured polymer-dispersed liquid crystals (nano-PDLCs) are transparent and optically isotropic materials in which submicron-sized liquid crystal (LC) domains are dispersed within a polymer matrix. Nano-PDLCs can induce birefringence by applying an electric field (E-field) based on the reorientation of the LC [...] Read more.
Nanostructured polymer-dispersed liquid crystals (nano-PDLCs) are transparent and optically isotropic materials in which submicron-sized liquid crystal (LC) domains are dispersed within a polymer matrix. Nano-PDLCs can induce birefringence by applying an electric field (E-field) based on the reorientation of the LC molecules. If nano-PDLCs are utilized as light-scattering-less birefringence memory materials, it is necessary to suppress the relaxation of the LC molecule orientation after the removal of the E-field. We focused on the ferroelectric smectic A (SmA) phase to suppress the relaxation of LC molecules, owing to its layered structure and high viscosity. Although nano-PDLCs require a strong E-field to reorient their LC molecules because of the anchoring effect at the LC/polymer interface, the required field strength can be reduced using a ferroelectric smectic A (SmAF) LC with a large dielectric constant. In this study, we fabricated a nano-PDLC by shining an ultraviolet light on a mixture comprised an SmAF LC, photocurable monomers, and a photo-initiator. The electro-birefringence effect was evaluated using polarizing optical microscopy. After the removal of the E-field, an enhanced memory effect was observed in the sample using SmAF LC compared with nematic LC-based nano-PDLCs. Full article
(This article belongs to the Special Issue Polymeric Liquid Crystals and Applications)
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27 pages, 6432 KiB  
Review
Supramolecular Arrangement and Conformational and Dynamic Properties of Chiral Smectic Liquid Crystals Obtained through Nuclear Magnetic Resonance: A Brief Review
by Valentina Domenici
Crystals 2024, 14(9), 823; https://doi.org/10.3390/cryst14090823 - 20 Sep 2024
Cited by 3 | Viewed by 1219
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Section Liquid Crystals)
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22 pages, 3912 KiB  
Review
Survey of Applicable Methods for Determining Viscoelastic Effects in Ferroelectric and Antiferroelectric Chiral Liquid Crystals
by Dorota Dardas
Materials 2024, 17(16), 3993; https://doi.org/10.3390/ma17163993 - 11 Aug 2024
Cited by 3 | Viewed by 1567
Abstract
Viscosity, elasticity, and viscoelastic properties are one of the most fundamental properties of liquid crystalline materials; the main problem in determining these properties is the multitude of physical parameters needed to determine the values of elasticity and viscosity constants. In this paper, a [...] Read more.
Viscosity, elasticity, and viscoelastic properties are one of the most fundamental properties of liquid crystalline materials; the main problem in determining these properties is the multitude of physical parameters needed to determine the values of elasticity and viscosity constants. In this paper, a number of different measurement methods for the complete characterization of viscoelastic properties for smectic liquid crystalline materials and their mixtures are analyzed, both theoretically and experimentally. The way in which viscoelastic material constants are determined depends mainly on the application/purpose of the materials under study. The subject of this work was to review the methods used to determine viscoelastic effects in ferroelectric and antiferroelectric chiral liquid crystals, their mixtures, composite materials, and even in dielectric systems, which would bear the hallmark of a universal method allowing the application of sufficiently low electric fields. In the case of chiral liquid crystals with ferroelectric and antiferroelectric phases and their subphases, the following assumption applies: fulfilment of Hooke’s law (in the case of elastic coefficients) and preservation of laminar flow (in the case of viscosity coefficients). Full article
(This article belongs to the Special Issue Liquid Crystals and Other Partially Disordered Molecular Systems)
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29 pages, 18161 KiB  
Review
Liquid-Crystalline Supermolecules Inducing Layer Fluctuations: From Hierarchical to Dissipative Structures
by Atsushi Yoshizawa
Crystals 2024, 14(8), 681; https://doi.org/10.3390/cryst14080681 - 26 Jul 2024
Cited by 2 | Viewed by 2348
Abstract
Liquid crystals, which have both liquid and solid properties, inevitably exhibit fluctuations. Some frustrated liquid-crystalline phases with a hierarchical structure, such as cybotactic nematic, modulated smectic, and bicontinuous cubic phases, are fascinating fluctuation-induced phases. In addition to these equilibrium phases, a pattern formation [...] Read more.
Liquid crystals, which have both liquid and solid properties, inevitably exhibit fluctuations. Some frustrated liquid-crystalline phases with a hierarchical structure, such as cybotactic nematic, modulated smectic, and bicontinuous cubic phases, are fascinating fluctuation-induced phases. In addition to these equilibrium phases, a pattern formation that is a nonequilibrium order through fluctuation is one of the most attractive research areas in soft matter. In this review, the studies on producing these fluctuation-induced orders in liquid crystals are described. Liquid-crystalline supermolecules in which several mesogens are connected via a flexible spacer have been designed. They have not only a characteristic shape but also an intra-molecular dynamic order. The supermolecules induce the fluctuations in layer structures at a molecular level, producing from the frustrated hierarchical to dynamic dissipative structures. In addition to reviewing molecular design for the hierarchical structures, the pattern propagation in a smectic phase is discussed based on the rotation of smectic blocks through Rayleigh–Bénard convection. Full article
(This article belongs to the Special Issue Advances in Liquid Crystal Dimers and Oligomers)
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16 pages, 3995 KiB  
Article
Density Functional Theory Calculations for Interpretation of Infra-Red Spectra of Liquid Crystalline Chiral Compound
by Aleksandra Deptuch, Natalia Górska, Michaela Murzyniec, Monika Srebro-Hooper, James Hooper, Magdalena Dziurka and Magdalena Urbańska
Crystals 2024, 14(7), 645; https://doi.org/10.3390/cryst14070645 - 13 Jul 2024
Cited by 1 | Viewed by 1877
Abstract
The experimental IR spectra of (S)-4′-(1-methylheptyloxycarbonyl) biphenyl-4-yl 4-[2-(2,2,3,3,4,4,4-heptafluorobutoxy) ethyl-1-oxy]-2-fluorobenzoate in the crystal phase are analyzed with the help of dispersion-corrected density functional theory (DFT+D3) calculations for isolated molecular monomer and dimer models, and a periodic model computed at the extended density [...] Read more.
The experimental IR spectra of (S)-4′-(1-methylheptyloxycarbonyl) biphenyl-4-yl 4-[2-(2,2,3,3,4,4,4-heptafluorobutoxy) ethyl-1-oxy]-2-fluorobenzoate in the crystal phase are analyzed with the help of dispersion-corrected density functional theory (DFT+D3) calculations for isolated molecular monomer and dimer models, and a periodic model computed at the extended density functional tight-binding (xTB) level of theory. It is found that the frequency scaling coefficients obtained with the results of the molecular calculations are good matches for the crystal phase, being close to 1. The molecular and periodic models both confirm that varied intra- and intermolecular interactions are crucial in order to reproduce the broadened shape of the experimental band related to C=O stretching; the key factors are the conjugation of the ester groups with the aromatic rings and the varied intermolecular chemical environments, wherein the C=O group that bridges the biphenyl and F-substituted phenyl groups seems particularly sensitive. The C=O stretching vibrations are investigated as a function of temperature, covering the range of the crystal, smectic CA*, smectic C* and isotropic liquid phases. The structure changes are followed based on the X-ray diffraction patterns collected in the same temperatures as the IR spectra. The experimental and computational results taken together indicate that the amount of weak C=O…H-C hydrogen bonds between the molecules in the smectic layers decreases with increasing temperature. Full article
(This article belongs to the Special Issue Liquid Crystal Research and Novel Applications in the 21st Century)
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