Liquid Crystal Dimers Research Articles

Synthesis and mesomorphic behaviour of new disulphide bridge 4-n-alkoxybenzylidine-4′-bromoaniline

Six members of homologues series of the liquid crystal dimers, 4-n-alkoxybenzylidine-4′-bromoaniline disulphides, which contain a sulphur–sulphur (S–S) link in the flexible spacer have been synthesised and their liquid crystalline properties were characterised. The dimers possess a general formulation in which a S–S group situated between two identical bromo-substituted aromatic imines have bonded, respectively, to S atom through the methylene unit of –(CH2)n– in which n denotes the number of carbon atoms. The number of carbon atoms in the spacers were varied following ascending order from 3 to 8. The dimers with a shorter spacer (n = 3 and 4) displayed nematic phase as well as smectic phase. The higher homologues in which n = 5–8 exhibited smectogens. The odd–even effect can be ascribed to the torsion angle of S–S linkage.

Novel luminescent liquid crystalline polyazomethines. Synthesis and study of thermotropic and photoluminescent properties

Novel semiflexible polyazomethines containing chromophoric units into azomethine mesogenic core have been synthesised by condensation of a flexible dialdehyde with mesogenic diamines containing fluorene, antraquinone, pyrimidine, azobenzene and benzophenone. The thermotropic behaviour of the resulting polyazomethines was assessed by differential scanning calorimetry, polarised light microscopy and investigations of the miscibility relations. While the pure polyazomethines showed a birefringent viscous texture difficult to be ascribed, by mixing with a liquid crystal dimer, clear Schlieren or marbled textures were observed, indicating a nematic mesophase. The polymers exhibited violet, blue or yellow light emission.

Phases and properties of nanocomposites of hydrogen-bonded liquid crystals and carbon nanotubes

We investigated a series of nanocomposites, built of the hydrogen-bonded liquid crystal (LC) p-n-heptyloxybenzoic acid (7OBA) and single-walled carbon nanotubes (SWCNTs) by optical microtexture analysis and other complementary methods. The surface orientation strength of the LC cell and the bulk interaction of the dimeric LC molecules with the SWCNTs turn out to mainly govern the type (symmetry), thermal stability, and chirality of the LC states induced in these nanocomposites. As a result, a cascade of phase transitions and phases not typical for pristine 7OBA were observed and additionally confirmed by temperature-dependent Raman spectroscopy and differential scanning calorimetry. The most effective SWCNT concentrations in the LC matrix, ensuring both the necessary conformability between these materials and induction of liquid crystal phases with unique optical and electro-optical properties, were found to be in the range of 0.01-0.007 wt%. Reversal of smectic phases into reentrant nematic states as well as induction of chirality in all LC phases were observed in the SWCNT-7OBA nanocomposite, even though pure 7OBA is typically achiral. However, our most intriguing result is the detection below the reentrant nematic of a triclinic smectic-C(G) phase, which is chiral and biaxial, and exhibits bulk ferroelectricity.

Mesogenic behaviour of p-nitrophenyl group linked with biphenyl mesogens via flexible spacers

Three series of nematogens with a terminal p-nitrophenyl group linked with biphenyl groups via flexible spacers were synthesised and their transitional properties were studied by means of differential scanning calorimetry (DSC) and polarising microscopy (POM). The nematic–isotropic transition temperature and the associated entropy change showed an odd–even effect as the length of the spacers was varied, in which the even members exhibited higher values. Such an odd–even effect was in consistency with the feature of liquid crystal dimers and trimers. On the basis of these data, it seemed reasonable to assume that the terminal p-nitrophenyl group played a role of mesogen in the nematic liquid crystal. The p-nitrophenyl group may work as a mesogen as a result of the interaction with the biphenyl mesogens. The mesogenic behaviour of the terminal p-nitrophenyl group is explained on the basis of neighbouring group effect.

Chemically induced twist-bend nematic liquid crystals, liquid crystal dimers, and negative elastic constants

Here we report the chemical induction of the twist-bend nematic phase in a nematic mixture of ether-linked liquid crystal dimers by the addition of a dimer with methylene links; all dimers have an odd number of groups in the spacer connecting the two mesogenic groups. The twist-bend phase has been identified from its optical texture and x-ray scattering pattern as well as NMR spectroscopy, which demonstrates the phase chirality. Theory predicts that the key macroscopic property required for the stability of this chiral phase formed from achiral molecules is for the bend elastic constant to tend to be negative; in addition the twist elastic constant should be smaller than half the splay elastic constant. To test these important aspects of the prediction we have measured the bend and splay elastic constants in the nematic phase preceding the twist-bend nematic using the classic Frederiks methodology and all three elastic constants employing the dynamic light scattering approach. Our results show that, unlike the splay, the bend elastic constant is small and decreases significantly as the transition to the induced twist-bend nematic phase is approached, but then exhibits unexpected behavior prior to the phase transition.

Flexoelectrically Driven Electroclinic Effect in the Twist-Bend Nematic Phase of Achiral Molecules with Bent Shapes

We extend the twist-bend nematic (N(TB)) model to describe the electro-optics of this novel phase. We predict an electroclinic effect (ECE) subject to a dc electric field E applied perpendicular to the helix axis or wave vector q, with rotation of the N(TB) optic axis around E. This linear effect, with its flexoelectric origin, is a close analog to the electro-optic effects observed for chiral liquid crystals. However, in nematics composed of achiral molecules having a bent shape, it is the electro-optic signature of the N(TB) phase. We test our model experimentally in the low-temperature nematic phase of the odd liquid crystal dimer, CB7CB, with its molecules having, on average, a bent shape. The ECE measurements confirm the previously proposed twist-bend nematic structure of this phase, with its broken chiral symmetry, extremely short (<10 nm) doubly degenerate pitch and ultrafast, submicrosecond response times.

A Comparison of the Conformational Distributions of the Achiral Symmetric Liquid Crystal Dimer CB7CB in the Achiral Nematic and Chiral Twist-Bend Nematic Phases

The sets of residual dipolar couplings between carbon and hydrogen nuclei obtained from the proton-encoded (13)C 2D NMR experiment are used to investigate the conformational changes which occur when the achiral symmetric liquid crystal dimer CB7CB changes from the achiral nematic to the chiral twist-bend nematic phase. It is found that these changes are a consequence of the chirality of the twist-bend nematic phase, rather than being the driving force for the stability of this phase.

Chiral solutes can seed the formation of enantiomorphic domains in a twist-bend nematic liquid crystal

The twist-bend nematic, an enantiomorphic liquid-crystalline phase, exhibited by the structurally symmetric liquid-crystal dimer CB7CB is induced to form a single domain of uniform handedness, in the bulk, by the addition of the dopant chiral solute (S)-1-phenylethanol. Addition of a nonracemic (or scalemic) mixture of both R and S enantiomers of this solute produced equal volumes of P and M chiral domains for the twist-bend nematic phase. This seeding of the domains in an enantiomorphic nematic conglomerate is revealed using deuterium NMR spectroscopy.

Optimizing the SmCP phase bent-core mesogen characteristics by introducing dimeric liquid crystals

This article demonstrates a method to simultaneously enhance the electro-optical properties and decrease the mesophase temperature of MD-H bent-core liquid crystals by introducing organosiloxane dimeric liquid crystals, C11Si2C11 and C11Si3C11. The differential scanning calorimetry, spontaneous polarization, and switching time were systematically studied. It has been shown that the MD-H bent-core liquid crystals doped with 20% dimeric liquid crystals have lower mesogen temperatures, faster switching times, and lower rotational viscosities.

Synthesis and mesomorphic properties of chiral liquid crystal dimers derived from azobenzene and substituted naphthol

Symmetrical liquid crystal dimers bis{2-alkyl-(S)-(+)-2-(6-[4-4′-decyloxyphenylazo)-benzoyloxy]-2-naphthyl)propinate} have conveniently been designed, synthesised and their mesomorphic properties were investigated. These dimers possess two identical mesogenic units with each of them attached to the terminal end of a flexible spacer (–C n H2n ; where n = 6–10). The respective mesogenic unit was made up from a naphthyl ring attached to the alkyloxylated azobenzene via the ester (COO–) bond. The chiral moiety attached to the 6-position of the naphthyl ring possesses a terminal carboxylic group COO– which linked up the mesogenic unit and the spacer. The thermal and optical properties for the ultimate compounds at different temperature were studied explicitly with the aids of differential scanning calorimetry and polarising optical microscopy. All dimers exhibit unambiguously the monotropic nematic and smectic A phases. The homeotropic alignment of the molecules within the anisotropic region was further confirmed through the application of homogeneously treated cell.

Cholesterol-based dimeric liquid crystals: synthesis, mesomorphic behaviour of frustrated phases and DFT study

Chiral unsymmetrical dimeric liquid crystals consisting of a cholesterol moiety as chiral entity and a substituted salicylidene imine core (with the substituent being butyl or fluoro or chloro group) interconnected through an even methylene spacer have been synthesised and their mesomorphic properties are characterised. All the dimers exhibit enantiotropic mesophases. The butyl homologue exhibited N* phase only, the fluoro- and chloro-substituted compound exhibited frustrated blue phases (BPs), N* phase and SmC* or twisted grain boundary (TGB) phases. The occurrence of a fluid frustrated phase, the BP, in particular, observed in compounds with a polar moiety and bent optimised conformation by density functional theory (DFT) study, indicates the importance of polar structures and bent shape of the compounds. Theoretical calculation was performed in order to study the optimised conformation, polarity and electron density distribution of the synthesised cholesterol derivatives using DFT. Time-dependent density functional theory (TD-DFT) calculation also had been carried out to investigate the absorption spectra and HOMO–LUMO energies. The experimental and theoretical absorption spectra are also presented.

Enlarged helical twisting power in chiral cyclic dimers based on conventional chiral alkyl diols

We prepared a homologous series of chiral cyclic liquid crystal (LC) dimers containing two biphenyl mesogens linked by two alkyl spacers, one of which was based on a R-enantiomeric chiral diol. In solution, the circular dichroism spectra of all the R-enantiomeric dimers showed the first negative and second positive Cotton effects, which indicated that the two biphenyl mesogens were located in a skewed overlapping alignment with counter-clockwise helicity. The helical twisting power (HTP) of these cyclic dimers was confirmed by the cholesteric LCs in mixtures with the nematic host. The induced cholesteric LCs in all mixtures had the same counter-clockwise helical sense as the skewed conformation of the two biphenyl mesogens. Furthermore, HTP values and Cotton effect amplitudes were linearly correlated, indicating direct induction of cholesteric twisting by the skewed biphenyl moieties. The induced HTP values were quite large, irrespective of the use of conventional chiral diols; the largest HTP value exceeded 100 μm−1 and was obtained in the cyclic dimer based on the R,R-1,2-diphenylethane diol.

Observation of a chiral smectic C phase over a wide thermal range with novel phase sequences in rigid, bulky chiral dimers

Four new, non-symmetric, optically active, liquid crystal dimers in which cholesterol and three-ring salicylaldimine mesogenic cores are interlinked through a flexible even-parity (ω-oxyalkanoyloxy) spacer have been synthesized and characterized by polarising optical microscopy, differential scanning calorimetry, electrical switching and X-ray diffraction. All the dimers, which differ from each other in the lengths of the central spacers (n = 3 and 5) and the terminal alkoxy chains (m = 20 and 22), exhibit a thermodynamically stable chiral smectic C phase over an unprecedented (100–180 °C) thermal range in novel phase sequences. Notably, the electrical switching study suggests the ferrielectric nature of the chiral smectic C phase originating arguably due to equally strong competition between ferroelectric and antiferroelectric ordering. The occurrence of such a mesophase in mesogens synthesized in this study is especially noteworthy as they comprise a bulky, rigid cholesterol entity.

Synthesis and Mesomorphic Properties of Uncoordinated Liquid Crystal Dimers Bis[4-[(4′-Decyloxyphenyl)Carboxylate]Salicylideneimino] Alkanes and Their Copper(II) Complexes

Series of symmetrical liquid crystal dimers wherein the spacer connected to two mesogenic units of salicylideneimines consists of the aliphatic chain ‒(CH2)n‒ where n adopts even parity numbers from 2 to 10 have been synthesized and characterized. These dimers function as tetradentate ligands which possess strong affinity toward the Cu(II) ion leading to the formation of four-coordinated complexes with Cu‒N and Cu‒O modes. The uncoordinated dimers exhibit enantiotropic nematic as well as smectic C phases. However, the Cu(II) complexes behave predominantly as nematogens. Correlation study between the effect of variable spacer length and the mesomophic behaviors of these dimers along with their related Cu(II) complexes are reported. The Cu(II) complexes in which the ligands possess shorter spacers were seemed to exhibit higher thermal stability.

Enantiotopic discrimination and director organization in the twist-bend nematic phase

Extending a molecular field model for the orientational order in the nematic phase, we calculate the (2)H-NMR splittings for the achiral solute 8CB-d2 in the twist-bend nematic phase formed by the achiral liquid crystal dimer CB7CB. We give an explanation for the enantiotopic discrimination observed in the spectra and comparison with experimental data allows us to provide quantitative estimates of the order parameters (pitch and conical angle) that characterize the director modulation of the twist-bend nematic phase.

Optical properties of dimeric liquid crystals doped with single-walled carbon nanotubes

Well oriented distinct local single crystals were grown in smectic C liquid crystal (LC) (heptyloxybenzoic acid – 7OBA) using predefined orientation of the single-walled carbon nanotubes (SWCNT). The SWCNT/SiOx/ITO/glass surface is found to cause a substantial enlargement of the smectic C distinct local single crystals and to reinforce both surface memory effect and surface anchoring. We synthesized and examined a set of nanocomposites, built of LC with hydrogen-bonded in dimers molecules (7OBA) and SWCNT. We found that the surface orientation strength and the interaction of the dimeric molecules with the carbon nanotubes play a decisive role for the type (symmetry), thermal stability and chirality of the LC states induced in the nanocomposites. As a result, a set of phase transitions and new phases (chiral smectic C, reentrant nematic, reentrant chiral nematic and a unique low-temperature chiral biaxial fluid smectic phase CG) not typical for pristine 7OBA were found.

Orientational order parameter studies in two symmetric dimeric liquid crystals – an optical study

The optical technique developed by [W. Kuczynski, B. Zywucki, and J. Malecki, Determination of orientational order parameter in various liquid-crystalline phases, Mol. Cryst. Liq. Cryst. 381 (2002), pp. 1–19; B.J. Zywucki and W. Kuczynski, IEEE transactions on optical phenomena – The orientational order in nematic liquid crystals from birefringence measurements, Dielectr. Electr. Insul. 8 (2001), pp. 512–515] is fabricated and used to determine the orientational order parameter in two dimeric liquid crystalline compounds nematic and SmA phases of α,ω-bis(4-alkylanilinebenzylidene-4′-oxy)alkane (m.OnO.m) homologous series. The compounds studied are 5.O8O.5 and 5.O10O.5 which exhibit nematic and SmA, and nematic phases, respectively. The orientational order parameter in both the phases of nematic and SmA phases of the compound one and the nematic phase of the compound two are obtained using the principle of Newton's rings which gives directly the birefringence, δn of the liquid crystal dimer. The merits of the technique used are presented over the conventional techniques for the determination of orientational order parameter. The results for the two compounds are compared with those values estimated from n e, n o and density using the two internal field models due to Vuks and Neugebauer applicable to nematic phase.

Odd–Even Effect of Dopant Molecules on Clearing Temperatures of Nematic Liquid-crystal Phases

Abstract Nematic liquid-crystal phases doped with the novel dopant compounds 1 (C6F5COO(CH)nOCOC6F5, n = 1–7) and 2 (C6H5COO(CH)nOCOC6H5, n = 1–7) showed an “opposite odd–even effect” on clearing temperatures. The tendency was exactly opposite to that reported for liquid-crystal dimers. A mechanism is postulated on the basis of the difference in the formation of molecular aggregations of even- and odd-number-dopant molecules in the host liquid-crystal molecules.

Synthesis and Characterization of Nonsymmetric Liquid Crystal Dimer Containing Biphenyl and Azobenzene Moiety

Calamitic liquid crystalline dimer containing azobenzene moiety and a decyloxy biphenyl linked by flexible spacers {4‐[7‐(4′‐decyloxy‐biphenyl‐4‐yloxy)‐alkyloxy]‐phenyl}‐(4‐decyl‐phenyl)‐diazene has been synthesized and characterized by spectroscopic methods. The transition temperatures and phase behaviours were studied by Differential Scanning Calorimeter (DSC) and Polarizing Optical Microscope (POM). The synthesized compounds exhibited enantiotropic liquid crystal phase with higher spacer display nematic and smectic C phases while lower spacer shows nematic and smectic A phases.

Dielectric relaxation study of a H shaped liquid crystal dimer

The present article reports dielectric relaxation study of an unusual shaped liquid crystal dimer (H shape) in the temperature range 40–85°C. The study of this liquid crystal dimer is important due to the presence of azo central linkage, which is photosensitive. The dielectric relaxation study indicates coupling between the electric field and the liquid crystal molecule of H shaped dimer. Various dielectric properties for this liquid crystal dimer are quite different from the conventional liquid crystals. The dielectric relaxation observed in the smectic phase is due to the reorientation of molecule along the director in the presence of an applied electric field. The temperature dependence of the dielectric parameters, such as relaxation frequency, relaxation strength and distribution parameter have been evaluated for this liquid crystal dimer for both planar as well as homeotropically aligned cell and then compared. The Cole–Cole equation has been used to evaluate the aforementioned parameters.