Chiral Liquid Crystalline Compounds Research Articles

Investigation of infra-red spectra of three chiral liquid crystalline compounds with different fluorosubstitution of benzene ring

The IR spectra of three liquid crystalline compounds, differing only by the number of fluorine atoms in the molecular core, are investigated. The DFT+D3/BLYP-def2SVP calculations for isolated molecules are applied for the band assignments of the experimental IR spectra collected in the crystal phase. Additional DFT calculations, including the B3LYP exchange-correlation functional and def2TZVPP basis set, are also performed for the compound without the fluorine atoms in the molecular core. The scaling factors between the experimental and calculated peak positions, obtained at different levels of theory, are compared. For all compounds, the absorption bands assigned to the C=O stretching vibrations are analyzed as a function of temperature in the isotropic liquid, smectic phases, and crystal phase. The formation of hydrogen bonding involving the C=O groups during crystallization is inferred. The differences in the crystallization temperature of three compounds and the presence of the hexatic smectic phase for only one compound are discussed.

Crystallization kinetics of (S)-4'-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[4-(2,2,3,3,4,4,4-heptafluorobutoxy)but-1-oxy]-2-fluorobenzoate.

Chiral liquid crystalline compounds belonging to the homologous series of (S)-4'-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[m-(2,2,3,3,4,4,4-heptafluorobutoxy)alk-1-oxy]-2-fluorobenzoates show various behaviors on cooling depending on the length of the CmH2m chain. The homologue with m = 2 crystallizes, while for m = 5, 6, 7, and presumably also for m = 3, the glass of the anticlinic smectic CA* phase is formed. The previous results for m = 4 suggest that this homologue may also be a glassformer. This paper presents the study of the crystallization kinetics for the compound with m = 4 in isothermal conditions (by polarizing optical microscopy) and for the 5-40 K min-1 cooling rates (by differential scanning calorimetry). Microscopic observations enable estimation of the energy barrier for nucleation, which equals 409 kJ mol-1. The threshold cooling rate necessary for complete vitrification of the smectic CA* phase, obtained by extrapolating the enthalpy change during crystallization to zero, is equal to 81 K min-1 or 64 K min-1 for the linear and parabolic fits, respectively. The structural studies by X-ray diffraction show that crystal phases have lamellar structures both in the pristine sample and after crystallization from the melt but with different layer spacing. A weak relaxation process is detected in the sample after melt crystallization, revealing the presence of the conformational disorder. The dynamic glass transition temperature of the SmCA* phase, estimated from the relaxation time of the PH process (as the α-relaxation time could not be registered in a wide enough temperature range), is 244 K.

Thermodynamic model to study the structural and electro-optical properties of chiral antiferroelectric smectic C phase exhibited by mesogenic homologous series 3FnHBM6(s) and W-316 mixture

ABSTRACT Using a thermodynamic model developed by us to study the structural and electro-optical properties of Sm C A ∗ phase, we investigate the temperature dependence of helical pitch, tilt angle and spontaneous polarization of a homologous series of fluorinated biphenyl benzoate esters (3FnHBM6, n = 2, 5, 7) and one of the series W-316-3 obtained from the mixture of two chiral liquid crystalline compounds 6F2OBi and 3F6HBM6. The free-energy density of the system exhibiting Sm C A ∗ phase is written as an expansion series in terms of all the relevant degrees of freedom: Q i j , ψ, P, q and the resulting coupling terms between these order parameters. The values of Landau coefficients are determined from the experimental data of antiferroelectric mesogens 3FnHBM6 (n = 2, 5, 7) and W-316-3 in the Sm C A ∗ phase. Using these coefficients, the electro-optical and structural properties have been studied. We have found good agreements between the theoretical and experimental results.

Phase Sequence, Kinetics of Crystallization and Molecular Dynamics of the Chiral Liquid Crystalline Compound Forming a Hexatic Smectic Glass

The vitrification of the antiferroelectric hexatic smectic XA* phase and cold crystallization are reported for (S)-4′-(1-methylheptylcarbonyl)biphenyl-4-yl 4-[5-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]benzoate. The kinetics of isothermal cold crystallization and melt crystallization are investigated, revealing that both are controlled mainly by diffusion, as indicated by decrease in the characteristic crystallization time with increasing temperature of crystallization, with an activation energy of 114 kJ/mol. A weak relaxation process is detected in a crystal phase, with an activation energy of 38 kJ/mol, implying the conformationally disordered crystal phase. The estimated fragility parameter of the investigated glass former is equal to 94.5, which indicates rather high fragility.

Comparative study of crystallization of two fluorinated chiral liquid crystalline compounds differing by fluorosubstitution of the molecular core

Crystallization and polymorphism of the crystal phases of two chiral liquid crystalline compounds exhibiting the antiferroelectric smectic CA* phase, one fluorosubstituted in the aromatic molecular core, are investigated by differential scanning calorimetry and X-ray diffraction. The fluorosubstituted compound starts crystallizing at smaller undercooling for a low cooling rate (2 °C/min), while for fast cooling (5–20 °C/min) and in isothermal conditions after fast cooling (20 °C/min) the crystallization of the non-fluorosubstituted compound occurs faster. Differences in the crystallization kinetics are discussed based on the thermodynamic properties as well as the molecular dynamics investigated for these compounds in the previous papers.

Investigation of a partially fluorinated chiral antiferroelectric liquid crystalline material with large negative dielectric anisotropy

Liquid crystal is a state of matter that has both liquid-like fluidity and crystal-like ordering in varying degrees. In this work, we study 4-{[(2S)-octan-2-yloxy]carbonyl}phenyl4′-{4-[(2,2,3,3,4,4,4-heptafluorobutanoyl)oxy]butoxy}-[1,1′-biphenyl]-4-carboxylate, a partially fluorinated chiral liquid crystalline compound. The mesomorphic studies of the compound highlight the existence of polar smectic phases. The molecular geometry, chemical reactivity, nonlinear optics, and charge dynamics are investigated by density functional theoretical calculations. The structural characterization of the compound is performed through vibrational spectroscopy. Dielectric spectroscopy highlights five collective relaxation processes that perfectly fit the modified Cole-Cole relaxation model. The compound 3F4Bi exhibits a bandgap of 4.05 eV, high birefringence (0.16), optical nonlinearity, and a large negative dielectric anisotropy for the tilted ferroelectric phase. The compound could be used as an optically active component to form ferroelectric multi-component mixtures.

Self-Assembling Behavior of Smart Nanocomposite System: Ferroelectric Liquid Crystal Confined by Stretched Porous Polyethylene Film.

The control and prediction of soft systems exhibiting self-organization behavior can be realized by different means but still remains a highlighted task. Novel advanced nanocomposite system has been designed by filling of a stretched porous polyethylene (PE) film with pore dimensions of hundreds of nanometers by chiral ferroelectric liquid crystalline (LC) compound possessing polar self-assembling behavior. Lactic acid derivative exhibiting the paraelectric orthogonal smectic A* and the ferroelectric tilted smectic C* phases over a broad temperature range is used as a self-assembling compound. The morphology of nanocomposite film has been checked by Atomic Force Microscopy (AFM). The designed nanocomposite has been studied by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), small and wide-angle X-ray scattering and broadband dielectric spectroscopy. The effect of a porous PE confinement on self-assembling, structural, and dielectric behavior of the chiral LC compound has been established and discussed. While the mesomorphic and structural properties of the nanocomposite are found not to be much influenced in comparison to that of a pure LC compound, the polar properties have been toughly suppressed by the specific confinement. Nevertheless, the electro-optic switching was clearly observed under applied electric field of low frequency (210 V, 19 Hz). The dielectric spectroscopy and X-ray results reveal that the helical structure of the ferroelectric liquid crystal inside the PE matrix is completely unwound, and the molecules are aligned along stretching direction. Obtained results demonstrate possibilities of using stretched porous polyolefins as promising matrices for the design of new nanocomposites.

Dielectric Properties of Chiral Ferroelectric Liquid Crystalline Compounds with Three Aromatic Rings Connected by Ester Groups

The tilted ferroelectric SmC* phase of three structurally different series having three aromatic rings in the core structure connected by ester groups with different end alkyl chain lengths, all of which are derived from lactic acid, have been observed by broadband dielectric spectroscopy. Introduction of structural variations within the liquid crystalline compounds has led to the formation of chiral nematic N*, or the paraelectric orthogonal SmA* phase at higher temperatures. The dielectric spectra strongly depend both on the temperature as well as the specific molecular structure of the self-assembling compounds possessing the ferroelectric polar order. The results reveal a strong Goldstone mode in the ferroelectric SmC* phase with ~kHz relaxation frequency. In the SmC* phase, the real and imaginary parts of the complex permittivity increase up to certain temperature near the SmC*-N*/SmA* transition and then decrease with increasing temperature, perhaps due to the disruption of the molecular domains at the onset of the SmA*/N* phase transition. The dielectric strength attains a maximum value in the SmC* phase and then decreases near the SmA*/N* phase transition. The dielectric strength is also influenced by the lengths of the alkyl chain and the nature of the connecting unit of the constituent molecules. The relaxation time and the relaxation frequency are found to vary with the molecular structure of the studied ferroelectric compounds.

Effect of molecular structure on dielectric and electro-optic properties of chiral liquid crystals based on lactic acid derivatives

Self-assembling behaviour of a few lactic acid derivatives with several ester linkage groups in the molecular core has been studied. The molecular structure–physical property correlations has been discussed in the light of the temperature dependences of the static permittivity, dielectric anisotropy, spontaneous polarization, response time and torsional bulk viscosity for eight chiral ferroelectric liquid crystalline compounds. Depending on the molecular structure these compounds exhibit the chiral nematic (N*) phase, the paraelectric orthogonal smectic A* (SmA*) phase and the ferroelectric tilted smectic C*(SmC*) phase being thermally stable over relatively broad temperature range. The temperature behaviour of the spontaneous polarization clearly confirms the second order nature of the SmA*-SmC* phase transition and the first order nature of the N*-SmC* phase transition. The effect of temperature and molecular configuration on the polarization and on the dispersion anchoring energy coefficients has been established. The obtained results are discussed in order to contribute to the structure – property relationship for the specific class of soft organic materials which can be used for design of smart multifunctional liquid crystalline mixtures aimed for optoelectronic and photonic applications.

Molecular Mobility Effect on Magnetic Interactions in All-Organic Paramagnetic Liquid Crystal with Nitroxide Radical as a Hydrogen-Bonding Acceptor.

We synthesized new chiral all-organic liquid crystalline (LC) compounds with nitroxide (NO) and hydroxy (OH) groups, which form intermolecular hydrogen bonds between the NO and OH groups. The LC compounds show hexagonal columnar phases at room temperature, which solidify as LC glasses at low temperature. The experimental magnetic susceptibility of each of the compounds in the LC and isotropic phases is larger than that theoretically estimated on the simple assumption about the amount of the spins, whereas it accords with the theoretical one in the LC glass state. It is called magneto-LC effects. The difference between experimental and theoretical magnetic susceptibilities gradually increases as temperature increases through the LC glass state-to-LC phase transition. It suggests that molecular mobility is one of the origins of the magneto-LC effects.

Influence of molecular structure on helicoidal structure and NMR spectra of chiral liquid crystalline esters

Three-ring chiral liquid crystalline compounds, forming antiferroelectric phase, differing in the structure of alkyl chain and in the substitution of benzene ring by fluorine atoms were studied. The measurements of helical pitch, based on the selective light reflection phenomenon, were performed as well as 1H and 13C NMR spectra at room temperature were registered. The influence of molecular structure as well as the type of helicoidal structure on the chemical shift of signals coming from chiral center was observed. Keywords: liquid crystals, helicoidal structure, nuclear magnetic resonance, antiferroelectric phase

Filaments in the twist-grain-boundary smectic-A phase.

A model of filaments of the twist-grain-boundary smectic-A phase (TGBA) arising from the homeotropic smectic-A phase and nucleating on the sample surface is proposed. The model is based on the concept of finite blocks of parallel smectic layers forming a helical structure. The blocks are surrounded by dislocation loops. The model describes the filament structure near the sample surface and the observed inclination of the filament axis with respect to the easy direction of the molecular anchoring on the surface. The model is based on the observations of filament textures of the TGBA phase in a chiral liquid crystalline compound, but can be applied for forming of TGBA filaments in any compound. The compression modulus of the compound has been estimated using such parameters as anchoring energy, estimated from the field necessary to transform the structure into the homeotropic smectic-A.

New chiral liquid crystal with unconventional dioxane terminal unit

While designing new chiral self-assembling materials, i.e. those possessing the liquid crystalline behaviour, special attention should be paid to the specific architecture of different molecular parts, in particular: molecular core, linkage groups, type and place of the lateral substituents, structure of the chiral centre and the chiral and non-chiral chains. For the first time a new chiral photosensitive liquid crystalline compound possessing an unconventional 1,3-dioxanylmethyl terminal unit attached to the non-chiral chain has been designed and synthesized. On cooling from the isotropic phase, the material possesses only one tilted liquid crystalline phase, namely the smectic I* phase with hexagonal ordering. The crystal phase has been detected at lower temperatures. The self-assembling and structural behaviour have been studied by different techniques and compared to that of the materials with similar molecular structure but possessing structurally different terminal units in the non-chiral chain.

Hexatic and blue phases in a chiral liquid crystal: optical polarizing microscopy, synchrotron radiation and dielectric study

Phase behavior, structure and molecular dynamics of a chiral liquid crystalline compound, which exhibits SmG*, SmJ*, SmF*, SmI*, SmC*, SmA*, N* and BP*, have been investigated. Observed optical textures, synchrotron radiation diffraction data and frequency dependent dielectric spectroscopic study clearly depict the temperature evolution of the different hexatic smectic phases along with cholesteric and blue phase in a single compound. In hexatic phases dielectric absorption spectra show one low frequency relaxation process, related to the phase fluctuation of the bond orientational order, and one high frequency process related to amplitude fluctuation of the bond orientational order coupled with the polarization and tilt of the molecules. Goldstone and soft mode relaxation processes are detected, respectively, in SmC* and SmA* phases.

Syntheses and Characterization of Chiral Branched-Arm Liquid Crystals-Basing on Isosorbide as Chiral Core

A new series of two-arm (MB1, MB2), four-arm (MB3), six-arm (MB4) chiral liquid crystalline compound containing isosorbide as chiral core were first synthesized. Four precursors of branched-arm B1~B4 were obtained at first and then were esterized separately with isosorbide and got four chiral branched-arm liquid crystals (MB1~MB4). The chemical structures and LC properties of the liquid crystalline molecule were measured by spectrum and thermal analysis techniques. XRD curves of MB1~MB4 samples only showed broad peaks at wide-angle, but no sharp peak was seen for all the samples. The results showed that MB1~MB4 appeared cholesteric phase with oily streak texture or lined texture and finger print texture. Isosorbide successfully induced cholesteric phase. The values of melting point and clearing point for MB1~MB4 decreased. The quantity of branched-arm and chiral core had effects on their liquid crystalline properties.

Pretransitional Layer Contraction at the Chiral Smectic A-to-Chiral Smectic C Phase Transition of a Chiral Nitroxide Radical

We have designed and synthesized a new chiral paramagnetic liquid crystalline compound with a nitroxide radical moiety showing chiral smectic A (SmA*) and C (SmC*) phases. This compound shows pretransitional layer contraction prior to the SmA*-to-SmC* phase transition in the cooling run. Electron paramagnetic resonance spectroscopy, X-ray diffraction analysis, and polarized optical microscopy reveal that a temperature-dependent conformational change is responsible for the pretransitional layer contraction.

Nanocomposite of superparamagnetic maghemite nanoparticles and ferroelectric liquid crystal

In this study we present a novel type of hybrid nanocomposite prepared by mixing maghemite nanoparticles and a chiral liquid crystalline compound. The hybrid system exhibits ferroelectric as well superparamagnetic properties. The impact of nanoparticles and the effect of an applied magnetic field on the ferroelectric liquid crystalline properties were established. The ferroelectric properties are conserved up to a concentration of 5.6% of maghemite. The magnetic behavior of the composites is typical for a system of superparamagnetic nanoparticles with inter-particle dipolar interactions and surface spin disorder.

The effect of different arms on the properties of chiral branched-arm liquid crystals based on isosorbide as the chiral core

A new series of two-arm ( MA1 , MA2 ), four-arm ( MA3 ) and six-arm ( MA4 ) chiral liquid crystalline compounds containing isosorbide as the chiral core were synthesised. Four precursors of branched-arm A1–A4 were first obtained, and then were esterised separately with isosorbide to obtain four chiral branched-arm liquid crystals ( MA1–MA4 ). The structure and properties have been characterised. The results show that MA1 was smectic–cholesteric phase with a fan-like and oily streak texture; MA2–MA4 showed a cholesteric phase with oily streak texture, or lined texture and finger print texture. Isosorbide successfully induced a cholesteric phase. The melting point and clearing point values for MA1–MA4 first increased and then decreased. The branched-arm and chiral core quantity affected the liquid crystalline properties. At the same time, the difference in side-arms resulted in different directions of rotation. MA1–MA2 showed right-handed rotation and had selective reflection; MA3–MA4 demonstrated left-handed rotation and did not have selective reflection.

Reentrant orthogonal smectic-Aphase below a tilted smectic-Cphase in a chiral compound

A reentrant orthogonal smectic-A (SmA) phase below the tilted smectic-C phase is established in a chiral liquid crystalline compound. The temperature evolution of the layer spacing confirms monolayer structure in both SmA phases, the upper SmA as well as the reentrant SmA phase. The reentrancy of the SmA phase is explained on the basis of the mean field free energy taking into account nonmonotoneous temperature dependence of the lowest term coefficient.

Chiral liquid crystalline compounds with a re-entrant SmA* phase

Download options Please wait... Supplementary files Supplementary information PDF (224K) Article information DOI https://doi.org/10.1039/C1JM12131F Article type Paper Submitted 13 May 2011 Accepted 01 Jul 2011 First published 15 Aug 2011 Download Citation J. Mater. Chem., 2011,21, 14807-14814 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Chiral liquid crystalline compounds with a re-entrant SmA* phase V. Novotná, V. Hamplová, N. Podoliak, M. Kašpar, M. Glogarová, D. Pociecha and E. Gorecka, J. Mater. Chem., 2011, 21, 14807 DOI: 10.1039/C1JM12131F To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author Vladimíra Novotná Věra Hamplová Natalia Podoliak Miroslav Kašpar Milada Glogarová Damian Pociecha Ewa Gorecka