Smectic A Research Articles

Non-symmetrical bent-core homologous series bearing 1,2,4-oxadiazole core with a cholesterol terminal arm: Synthesis, characterization and their liquid crystalline properties

Nonsymmetric 1,2,4-oxadiazole derivatives with cholesteryl and alkoxy chain as end moieties exhibiting monotropic liquid crystalline behavior have been reported. The molecular structures have been confirmed by elemental analysis and spectroscopic studies. Differential scanning calorimetry (DSC) studies revealed multiple phase transitions and polarized optical microscopy (POM) investigations confirmed smectic A (SmA) and chiral nematic (N*) phases. The importance of alkyl chain length in mesophase formation is discussed. A comparison with other reported mesogenic materials possessing similar molecular structures is also discussed.

Effect of Smectic Layers on Thermal Diffusivity of Side-Chain Polymer Liquid Crystals

The thermal conductivity (TC) of polymers is known to be effectively enhanced by liquid crystallinity. Liquid crystals (LCs) exhibit anisotropic TC with a greater magnitude in the orientation direction. However, the effects of other LC structures than the orientational order, such as smectic layer structures, on TC have not been well studied. This study investigated the correlation between LC structures and thermal diffusivity using a series of LC PMnMA polymethacrylates having azobenzene mesogens in the side chains. PMnMA formed nematic (N), smectic A (SmA), and smectic C (SmC) phases. These LCs were aligned by a magnetic field or large-amplitude oscillatory shear, yielding glassy LC films with mesogen long axes in the in-plane or out-of-plane direction. These glassy LCs increased thermal diffusivities in the LC orientation direction with the degree of LC orientation, whereas N and SmC LCs had smaller values than SmA LCs. These results demonstrated that smectic layers can enhance thermal diffusivity in their normal direction.

Front Cover: Magnetically Manipulable Ionic Liquid Crystals Incorporating Neutral Radical Moiety (ChemPlusChem 3/2022)

The front cover displays novel ionic liquid crystalline (ILC) compounds containing a nitroxide radical unit in the organic cations, showing an enantiotropic smectic A (SmA) phase. One of the ILC compounds shows strong intermolecular magnetic interactions owing to the nanosegregation of strongly bonded ionic and non-ionic moieties. Its droplet can be magnetically manipulable. More information can be found in the Full Paper by Yoshiaki Uchida, Rui Tamura, and co-workers.

Synthesis and DFT Investigation of New Low-Melting Supramolecular Schiff Base Ionic Liquid Crystals

Supramolecular, low-melting (near or below 0.0 °C) ionic liquid crystals with two rings of Schiff bases were prepared and studied. The Schiff bases were synthesized using 4-substituted aniline derivatives and 4-pyridine carbaldehyde and then mixed in equimolar amounts with linear 1-bromoalkanes of different chain lengths, namely C6, C8, and C14. The mesomorphic behavior and thermal properties of the compounds were determined by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). Only the ionic liquids analogous with 1-bromotetradecane exhibit mesomorphic behavior. All, except the smectic A (SmA) monomorphic fluorine-substituted complex, show dimorphic enantiotropic mesophases, namely SmA followed by nematic (N) mesophases depending on the temperature rise. The DSC and POM results for the induced mesophases were then treated with density functional theory calculations (DFT). The results showed that both the polarity of the polar groups and the length of the alkyl groups strongly influence the mesomorphic properties of the ionic liquids.

Mesomorphic properties of benzoxazole Salicylaldimines and their Copper(II) Complexes: Synthesis and structural characterization

A series of benzoxazole based 5-(alkoxy)-2-(((4-(5-methylbenzoxazol-2-yl-)- phenyl)imino)methyl)phenol, HLn (n = 10, 12, 14) and their copper(II) complexes had been synthesized; molecular structures of all the organic compounds and the metal complexes were elucidated by various spectroscopic techniques along with elemental analyses. Thermotropic properties were investigated by a combination of POM observation, DSC analysis and X-ray diffraction experiments. All members of the series exhibit enantiotropic smectic-A (SmA) mesophase. DFT calculations imply stable electronic structure of the ligand; HLn (n = 12) as well as of its copper(II) complex.

Aroyloxycinnamates with wide mesophase temperature ranges

ABSTRACT A new series of eight asymmetric homologues was designed and synthesised by the reaction of aroyloxybenzaldehydes with Wittig salt of methyl bromoacetate, where the length of the alkoxy chain was varied. All the compounds were found thermally stable up to 220°C. Differential scanning calorimetry, polarising optical microscopy and X-ray diffraction were used to study the mesomorphic properties, where a mesophase range of up to 80°C was obtained. The two shorter homologues with C3–C4 were nematic, the intermediate lengths were nematic and smectic A (SmA) with a progressive increase of the SmA domains and the longest homologue with C12 was purely SmA. The translational order parameter of the SmA mesophases showed that the molecular order inside the smectic layers increases with molecular length, associated with the higher stabilisation and predominance of the SmA phase. All compounds dispersed in solution absorb light in the ultraviolet region.

Cholesterol-based nonsymmetric dimers comprising phenyl 4-(benzoyloxy)benzoate core: the occurrence of frustrated phases

ABSTRACT The synthesis and mesomorphism of sixteen new nonsymmetric liquid crystal dimers formed by covalently attaching cholesterol with a three-ring mesogenic core, namely, phenyl 4-(benzoyloxy)benzoate, via an ω-oxyalkanoyl spacer are described. The lengths of the terminal chain attached to the three-ring core, as well as those of the ω-oxyalkanoyl spacer, have been varied; accordingly, they have been grouped into four sets. They display an enantiotropic chiral nematic (N*) behaviour with the isotropization temperature crossing over 200 oC. Four dimers having an odd-parity spacer were found to additionally show blue phase-I/II (BP-I/II), and the smectic A (SmA) phase. Twelve dimers with an even-membered spacer also stabilise either chiral smectic C (SmC*) or twist grain boundary (TGB) phase having SmC* slabs (TGBC* phase). The dimers with longer spacer and terminal tail favour the formation of the TGBC* phase. Thus, the lengths of both the terminal tail and the central spacer are seen to direct the type of mesophase and liquid crystal phase sequences to be formed. X-ray diffraction measurements have been carried out on representative samples to corroborate the structure of the mesophases. The N* phase has been probed with the aid of CD technique to figure out the handedness of the helicoidal structure.

Antibacterial Activity and Mesophase Identification of Azomethnine and Azo derivatives

A new mesogenic homologous series of liquid crystalline azomethnine and azo derivatives of 4ꞌ-nalkoxybenzylidiene- 4-aminoazobenzene has been synthesized and characterized by a combination of elemental analysis and standard spectroscopic methods. In the present series, nematic mesophase commences from n-propyloxy derivative as enantiotropic and persists up to the last member synthesized except in derivative C10. The smectic A (SmA) mesophases commences from n-pentyloxy derivative as enantiotropic and also persists up to ntetradecyloxy synthesized. Imine linkage (-CH═N-) between central and terminal benzene rings helping to understand the polarizability effect as well as nature of mesophase as stability gets reduced due to the presence of nitrogen in the ring. The mesomorphic properties of present series are of great importance to evaluate the effects of central linkage on mesomorphism. The mesomorphic properties of present series were compared with other structurally related mesogenic homologous series to evaluate the effects of central linkage on mesomorphism.

Synthesis, Phase Behavior and Computational Simulations of a Pyridyl-Based Liquid Crystal System.

A homologous set of liquid crystalline materials (Tn) bearing Schiff base/ester linkages were prepared and investigated via experimental and theoretical techniques. Terminal flexible groups of different chain lengths were connected to the end of phenylbenzoate unit while the other end of molecules was attached to the heterocyclic pyridine moiety. The molecular structures of the designed molecules were evaluated by FT-IR, NMR spectroscopic analyses, whereas their mesomorphic properties were investigated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). They all exhibited dimorphic properties with the exception of the members having the shortest and longest terminal flexible chains (n = 6 and 16), which were monomorphic. The T16 derivative was further found possessing purely smectic A (SmA) mesophase while others have their lengths covered by nematic (N) phase. Moreover, the computational evaluation of the azomethine derivatives was carried out using a DFT approach. The polarity of the investigated derivatives was predicted to be appreciably sensitive to the size of the system. Furthermore, the Frontier molecular orbitals analysis revealed various distributions of electron clouds at HOMO and LUMO levels.

Magnetically Manipulable Ionic Liquid Crystals Incorporating Neutral Radical Moiety.

With a view to fabricating a new remote input-output system by applying functional ionic liquid crystalline (ILC) materials, we have developed novel ILC compounds containing a nitroxide radical unit in the organic cations, which show an enantiotropic smectic A (SmA) phase. We have implemented the magnetic manipulation of a droplet of one of the ILC compounds on the basis of the intermolecular magnetic interactions between radical moieties. This ILC monoradical compound shows a 55 % larger increase in paramagnetic susceptibility at the solid-to-LC melting point in the first heating process than the non-ionic LC monoradical compounds. It is most likely owing to the nanosegregation of strongly bonded ionic and non-ionic moieties. The increased molar magnetic susceptibility is preserved not only in the SmA phase but also in the isotropic liquid and solid phases during the first cooling process.

Polar Alkoxy Group and Pyridyl Effects on the Mesomorphic Behavior of New Non-Symmetrical Schiff Base Liquid Crystals

A series of non-symmetrical Schiff base liquid crystals were prepared and investigated. Schiff bases of p-alkyloxy aniline derivatives and 4-phenyl pyridine-4′-carbaldehyde were synthesized. The terminal alkoxy groups substituting aniline are of varied chain length, namely C6, C8, and C16. The structures of the compounds were confirmed via 1H NMR and 13C NMR spectroscopy. Different mesophases of the samples were thermally and optically characterized by differential thermal analysis (DSC) and polarized optical microscopy (POM). All samples revealed enantiotropic smectic B (SmB) and smectic A (SmA) mesophases. The results obtained were further correlated with the density functional theory (DFT) theoretical calculations. The results are compared to a series of compounds bearing biphenyl moiety in their mesogens. The thermal stabilities of the different mesophase reduced upon the increment of the alkoxy chain length. The temperature ranges of both the smectic mesophases of new compounds bearing the 4-phenyl pyridine moiety are generally expanded higher than the other series. In addition, the total mesophase range is greater in the new compounds when compared to their biphenyl analogues. The DFT results were investigated in terms of the molecular geometries and the frontier molecular orbitals as well as the charge distribution mapping to show and illustrate the difference in the mesomorphic properties.

Defect Structures of Magnetic Nanoparticles in Smectic A Liquid Crystals.

Topological defects in anisotropic fluids like liquid crystals serve as a playground for the research of various effects. In this study, we concentrated on a hybrid system of chiral rod-like molecules doped by magnetic nanoparticles. In textures of the smectic A phase, we observed linear defects and found that clusters of nanoparticles promote nucleation of smectic layer defects just at the phase transition from the isotropic to the smectic A (SmA) phase. In different geometries, we studied and analysed creation of defects which can be explained by attractive elastic forces between nanoparticles in the SmA phase. On cooling the studied hybrid system, clusters grow up to the critical dimension, and the smectic texture is stabilised. The presented effects are theoretically described and explained if we consider the elastic interaction of two point defects and stabilisation of prismatic dislocation loops due to the presence of nanoparticles.

High-resolution investigation by Peltier-element-based adiabatic scanning calorimetry of binary liquid crystal mixtures with enhanced nematic ranges

High-resolution Peltier-element-based adiabatic scanning calorimetry (pASC) has been used to investigate the temperature dependence of the specific heat capacity and specific enthalpy of two mixture systems of the liquid crystal smectic A1 compound 5-n-nonyl-2-(4′-isothiocyanatophenyl)dioxane-1.3 (9DBT), and one of the smectic Ad compounds 4-n-octyloxy-4′-cyanobiphenyl (8OCB) and 4-nonyloxy-4′cyanobiphenyl (9OCB). For both mixture systems, measurements have been carried out over a large temperature range, from the crystalline solid phase over the smectic and nematic phases into the isotropic liquid phase. Both systems exhibit substantial, mixing-induced, enhanced nematic ranges and large changes in the composition dependence of the transition temperatures between the different phases. In both systems, eutectic melting points have been located and, for the different mixtures, the melting and eutectic transition heats have been obtained. The nematic to isotropic (NI) transitions are weakly first order with latent heat values in the range usually observed for this transition in other liquid crystals. The critical behavior of the specific heat capacity at the NI transition is described by exponent values near the tricritical one of 0.5. Along the smectic A to nematic (AN) transition lines, strong composition dependence was observed for the latent heat, from almost zero to values comparable to those observed at the nematic to isotropic transition. The concentration dependence of these AN latent heats was adequately fitted with a crossover function consistent with a mean-field free-energy expression that has a nonzero cubic term; the latter is induced by the Halperin-Lubensky-Ma coupling between the smectic A order parameter and orientational order director fluctuations. The fitting analysis resulted in the location of a Landau-tricritical point along one branch of the transition line in the system 9DBT-8OCB and one in each branch (for low and high 9OCB mole fractions) of the NA transition line of the 9DBT-9OCB system. The effective critical exponent values for the specific heat capacity of the AN transitions follow the McMillan ratio-dependence observed for other liquid crystal mixtures.

Topological Defect-Guided Regular Stacking of Focal Conic Domains in Hybrid-Aligned Smectic Liquid Crystal Shells

We study liquid crystal (LC) shells in hybrid configuration (director tangential to the inside but normal to the outside) as they slowly undergo a transition from a nematic (N) to a smectic-A (SmA) phase. Every shell has two antipodal +1 topological defects, at the thinnest and thickest points, respectively. On cooling from N to SmA, the symmetry axis connecting the defects gradually reorients from along gravity to perpendicular to it, reversibly and continuously, if the LC and aqueous phase are density matched at the N-SmA transition. This suggests reduced density near the defects—reflecting a local reduction in order—under the strong confinement with antagonistic boundary conditions. In the SmA phase, a regular array of focal conic domains (FCDs) develops, templated in position and orientation by the +1 defect at the thinnest point. Around this defect, a single complete toroidal FCD always develops, surrounded by incomplete FCDs. In contrast to similar FCD arrangements on flat aqueous interfaces, this is a stable situation, since the two +1 defects are required by the spherical topology. Our results demonstrate how the topological defects of LC shells can be used to template complex self-organized structures. With a suitable adaption of the LC chemistry, shells might serve as a basis for producing solid particles with complex yet highly regular morphologies.

Synthesis, Optical and DFT Characterizations of Laterally Fluorinated Phenyl Cinnamate Liquid Crystal Non-Symmetric System

A new laterally fluorinated unsymmetric liquid crystalline homologous series, based on cinnamate linkage, named 2-fluoro-4-(4-(alkoxy)phenyl)diazenyl)phenyl cinnamate (In), was synthesized and evaluated via different experimental and computational tools. The series had different terminal alkoxy-chain lengths with a lateral F atom in the meta position with respect to the azo moiety. The experimental mesomorphic and optical investigations were carried out using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Theoretical calculations and geometrical parameter predictions were conducted using the DFT program method at B3LYP/6-311G** level of theory. The results revealed that all the designed compounds exhibited the nematic (N) mesophase enantiotropically. The nematic stability and temperature range were impacted by the terminal alkoxy chain length. Compounds with the shortest chains (I6 and I8) showed a monotropic smectic A (SmA) phase, while the longest chain derivative, I16, possessed enantiotropic Sm A phase. Theoretical density functional theory (DFT) predictions were correlated with the practically observed data from the mesomorphic investigations. Data revealed that the terminal alkoxy and lateral F groups had an essential impact on the total energy of possible geometrical structures and their physical and thermal parameters.

Two-dimensional flow and linear stability properties of smectic A liquid crystals

We examine some leading-order flow and stability properties of smectic A (SmA) liquid crystals (LCs) in two spatial dimensions by analysing a fully nonlinear continuum theory of these materials. We derive a system of equations for the dynamic variables describing the flow velocity and orientation of the material under suitable assumptions upon these quantities. This system can provide insight into the leading-order behaviour under quite general circumstances, and we provide an example of utilising this system to determine the flow induced by a constant pressure gradient applied normally to the smectic layers. We then consider the effect of oscillatory perturbations on a relaxed, stationary sample of SmA, and provide criteria under which one would expect to see the onset of instability in the form of inequalities between the material parameters and perturbative wave number. We find that instability occurs for physically realisable values of these quantities, and, in particular, that certain viscosities characterising the SmA phase can act as ‘destabilising agents’ such that one could, for a given sample with known parameter values, manipulate the behaviour of that sample.

Making Smectic Defect Patterns Electrically Reversible and Dynamically Tunable Using In Situ Polymer-Templated Nematic Liquid Crystals.

Shaping liquid crystals (LCs) into arrays of defect patterns enables the design of composite materials with new stimuli-responsive properties. Self-assembled defect assemblies that may arise in layered smectic A (SmA) LCs such as focal conic domains (FCDs), exhibit remarkable optical features and abilities for ordering nanoparticles. However, such SmA defect patterns are essentially electrically irreversible, which currently limits their adjustability in a dynamic way. Here, in situ polymerization of the texture of SmA FCDs allows transferring them into more electrically responsive LC phases, such as nematic, making possible a dynamic switch between different textural and optical states of FCDs in a reversible manner with voltage. Moreover, the method readily enables to program the operating temperature range of the polymer/LC composite from its chemical composition, adapting the system to various potential uses. This approach may increment new applications of SmA defect patterns such as voltage-tunable privacy layers and may further inspire the design of LC-based nanostructured composite and hybrid materials with new functions that can be dynamically tuned with voltage.

New Nitro-Laterally Substituted Azomethine Derivatives; Synthesis, Mesomorphic and Computational Characterizations.

Two new homologues series, based on two rings of the azomethine central group bearing the terminal alkoxy group of various chain lengths, were prepared. The alkoxy chain length varied between 6 and 16 carbons. The other terminal wing in the first series was the F atom, and the compound is named N-4-florobenzylidene-4-(alkoxy)benzenamine (In). The second group of compounds included a lateral NO2 substituent in addition to the terminal F atom, named N-(4-fluoro-3-nitrobenzylidene)-4-(alkyloxy)aniline (IIn). Mesomorphic and optical properties were carried out via differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Elemental analyses, FT-IR, and NMR spectroscopy were carried out to elucidate the molecular structures of the synthesized groups. Mesomorphic investigations indicated that all the synthesized homologues (In) were monomorphic, possessing the smectic A (SmA) phase monotropically, while the second group (IIn) members were non-mesomorphic. The experimental data indicated that the formation of the mesophase is affected by the protrusion of the lateral nitro group. The disruption of the mesophase in the second group was attributed to the increase of its molecular width, which affects its lateral intermolecular interactions. The computational simulations were in agreement with the experimental data. On the other hand, the location of NO2 group within the molecular geometry increased the melting temperature of the molecule, and thus, affected their thermal and physical properties. By discussing the estimated parameters, it was found that the molecular architecture, the dipole moment, and the polarizability of the investigated compounds are highly affected by the electronic nature and position of the terminal and lateral substituents as well as their volumes.

Smectic Liquid Crystalline Polymer Membranes with Aligned Nanopores in an Anisotropic Scaffold.

Bottom-up methods for the fabrication of nanoporous polymer membranes have numerous advantages. However, it remains challenging to fabricate nanoporous membranes that are mechanically robust and have aligned pores, that is, with a low tortuosity. Here, a mechanically robust thin-film composite membrane was fabricated consisting of a two-dimensional (2D) porous smectic liquid crystalline polymer network inside an anisotropic, microporous polymer scaffold. The polymer scaffold allows for relatively straightforward planar alignment of the smectic liquid crystalline mixture, which consisted of a diacrylate cross-linker and a dimer forming benzoic acid-based monoacrylate. Polymerized samples displayed a smectic A (SmA) phase, which formed the eventual 2D porous channels after base treatment. The aligned 2D nanoporous membranes showed a high rejection of anionic solutes bigger than 322 g/mol. Cleaning and reusability of the system were demonstrated by intentionally fouling the porous channels with a cationic dye and subsequently cleaning the membrane with an acidic solution. After cleaning, the membrane properties were unaffected; this, combined with numerous pressurizing cycles, demonstrated reusability of the system.

Novel sulphonic acid liquid crystal derivatives: experimental, computational and optoelectrical characterizations.

A novel liquid crystal homologous series based on the benzene sulphonic acid moiety, namely (E)-4-((4-((4-(alkoxy)benzoyl)oxy)benzylidene)amino)benzenesulfonic acid (Sn), was synthesized and examined via different experimental and theoretical measurements. The four synthesized members have terminally connected alkoxy chain groups, which vary between 6 and 12 carbons. FT-IR and NMR spectroscopy, as well as elemental analyses, were used to confirm their molecular structures. Mesomorphic and optical investigations of the prepared homologues were also conducted using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The DSC and POM characterization revealed that all of the synthesized sulphonic acid members are monomorphic, exhibiting a pure smectic A (SmA) mesophase with enantiotropic properties. Moreover, all compounds in the group have high thermal transition temperatures. The terminal electron-withdrawing group –SO3H plays a considerable role in the stabilization of the molecule, which in return resulted in high thermal SmA stability. Furthermore, the experimental data relating to the mesophase behavior were substantiated via computational studies using the DFT approach. In addition, the terminal –SO3H moiety has an essential impact on the thermal and physical parameters of possible geometries. All members of the synthesized Sn series exhibit ohmic behavior with electrical resistance in the GΩ range, as revealed by electrical measurements. The S10 electrode had the highest electrical conductivity: 35.16 pS. It also showed two direct optical band gaps of 3.58 and 3.23 eV with Urbach energies of 1261.1 and 502.4 meV. Upon decreasing the number of carbon atoms to n = 6, the main bandgap for S6 reduced to 3.3 eV. The highest conductivity, good absorption, and two large bandgaps recorded for the chain derivative S10 make it suitable for investigations relating to energy-based applications.