Search Results (20)

The spontaneous formation of self-sorted columnar structures of electron-donating and accepting π-conjugated molecules is attractive for photoconducting and photovoltaic properties. However, the simple mixing of donor–acceptor discotic molecules usually results in the formation of mixed-stacked or alternating-stacked columns. As a new strategy for overcoming this problem, here, we report the “side-chain labeling” approach using binary discotic systems and realize the preferential formation of such self-sorted columnar structures in a thermodynamically stable phase. The demonstrated key strategy involves the use of hydrophobic and hydrophilic side chains. The prepared blend is composed of liquid crystalline phthalocyanine with branched alkyl chains (H₂Pc) and perylenediimide (PDI) carrying alkyl chains at one side and triethyleneglycol (TEG) chains at the other side (PDI_C12/TEG). To avoid the thermodynamically unfavorable contact among hydrophobic and hydrophilic chains, PDI_C12/TEG self-assembles to stack up on top of each other and H₂Pc as well, forming a homo-stacked pair of columns (self-sort). Importantly, H₂Pc and PDI_C12/TEG in the blend are macroscopically miscible and uniform, and mesoscopically segregated. The columnar liquid crystalline microdomains of H₂Pc and PDI_C12/TEG are homeotropically aligned in a glass sandwiched cell. The “labeling” strategy demonstrated here is potentially applicable to any binary discotic system and enables the preferential formation of self-sorted columnar structures. Full article

The electrochemical and spectroelectrochemical properties of the discotic mesogen 2,3,6,7,10,11-pentyloxytriphenylene (H5T) were studied with the use of cyclic voltammetry combined with UV-Vis and electron paramagnetic resonance (EPR) spectroscopy in solution. The UV-Vis absorption spectroscopy of H5T in dichloromethane showed its monomeric state in a concentration range up to 10⁻³ mol dm⁻³. The reversible process of the electrochemical formation of the radical cation was evidenced within the experimentally accessible potential window. The in situ UV-Vis spectroelectrochemical measurements further enabled identification of the product of the redox process and evaluation of the effect of aggregation in the concentration range of 5 × 10⁻³ mol dm⁻³. The results are discussed in the frame of solvent effects on the self-assembly propensity of solute molecules, in a wide range of concentrations. In particular, the crucial role of the solvent polarity is indicated, which contributes to the understanding of solution effects and pre-programming of supramolecular organic materials, in particular anisotropic disc-shaped hexa-substituted triphenylenes. Full article

Organic semiconductors are the focus of numerous studies; they are used in electronic devices. Modern research involves the production of neuromorphic organic materials, including those based on liquid crystal materials. The purpose of this work involves the theoretical modeling of molecules (the “core with branches” type) to construct a discotic mesophase capable of performing the functions of a neuromorphic material. For this purpose, the conductivity of crystal porphine, which can act as the nucleus of a molecule of the “core with branches” type, was investigated. The Marcus theory charge mobility values for the hole and electron were 0.148 and 0.088 cm²/V·s, respectively (the MOO method for calculating transfer integrals), and 0.561 and 0.160 cm²/V·s (DIPRO method). Based on TD-HF (HF-3c level of theory) calculations, possible structures of molecules for the formation of a discotic mesophase are proposed. Full article

Optical textures pictured in the seminal 1974 textbook, The Microscopy of Liquid Crystals, by Norman Hartshorne, have been reappraised. Some of these, which were described by Hartshorne (and many others) as confused focal conics, were of chromonic and discotic phases, which had not been identified at that time—and would now be recognized as developable domain structures of columnar phases. It is suggested that the rigorous constraint of isometry in these is relaxed in regions of the director field under high stress. A rationale for the characteristic striated appearance of columnar textures is proposed, in which the molecular columns are bundled together, forming twisted ropes within the domains. It is also suggested that the regular alternation of opposing domains in M ribbons minimizes the slippage of columns required as the mesophase develops, and an explanation of the characteristic multi-pole appearance of the brushes in the optical textures of columnar structures is proposed. Full article

Ordered interdigitated heterojunction as a promising nanostructure has attracted considerable attention due to its potential application in solar cells. However, a suitable construction to achieve effective free carrier transport in these nanostructures remains a challenge. In this study, interdigitated nanostructure was fabricated by combining vertically orientated TiO₂ nanotube array with discotic liquid crystal Copper (II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (tbCuPc). These discotic molecules were assembled as homeotropic alignment in the interdigitated nanostructure, which enhanced the carrier mobility of active layer considerably. The performance of photovoltaic cells with this interdigitated heterojunction was improved. Molecule orientation leading to charge carrier mobility enhancement was found to play a key role in improving the power conversion efficiency of the devices substantially. Full article

The objective of this study was to simulate the flow of graphene oxide (GO) dispersions, a discotic nematic liquid crystal (DNLC), using the Ericksen-Leslie (EL) theory. GO aqueous suspension, as a lubricant, effectively reduces the friction between solid surfaces. The geometry considered in this study was two cylinders with a small gap size, which is the preliminary geometry for journal bearings. The Leslie viscosity coefficients calculated in our previous study were used to calculate the stress tensor in the EL theory. The behavior of GO dispersions in the concentration range of 15 mg/mL to 30 mg/mL, shown in our recent experiments to be in the nematic phase, was investigated to obtain the orientation and the viscosity profile. The viscosities of GO dispersions obtained from numerical simulations were compared with those from our recent experimental study, and we observed that the values are within the range of experimental uncertainty. In addition, the alignment angles of GO dispersions at different concentrations were calculated numerically using EL theory and compared with the respective theoretical values, which were within 1% error. The anchoring angles corresponding to viscosity values closest to the experimental results were between 114 and 118 degrees. Moreover, a sensitivity analysis was performed to determine the effects of different ratios of the elasticity coefficients in EL theory. Using this procedure, the same study could be extended for other DNLCs in different geometries. Full article

Bent-core liquid crystals (BCLC) have been widely studied as a result of their unusual polar and chiral properties. Similar to calamitic and discotic molecules, BCLC molecules also exhibit nematic phases, besides other higher order mesophases. The aim of this work is to comparatively analyze the mesomorphic behavior of some bent-core 1,3-disubstituted benzene core compounds derived from resorcinol and isophthalic acid. Thus, the two classes of compounds differ in the nature of the orientation of the ester bond between the benzene central core and the two branches attached to the core. The mesomorphic behavior was elucidated by polarized light optical microscopy and differential calorimetry. Given the relatively high isotropic points of the compounds, confirmation of the thermal stability in the domains manifesting liquid crystalline properties was performed by thermogravimetric studies. The theoretical explanation of the difference in mesomorphic behavior for the two classes was based on molecular modeling studies. Full article

Star-shaped compounds are widely recognized as emerging materials for optical and electrical applications and as scaffolds of discotic liquid crystal. While the C₃-symmetrical tri(phenylthienyl)benzene is the core for several electroopotical materials, no liquid crystal with this scaffold has yet been reported. Acid-catalyzed cyclocondensation of bromoacetylthiophene gives a C₃-symmetrical star, threefold Suzuki coupling results in extension of the conjugated system. With 3,4-didodecylocyphenyl boronic acid, a star with a large rigid conjugated system and flexible aliphatic periphery is obtained. Differentials scanning calorimetry and polarized optical microscopy reveal an enantiotropic mesophase from 66 °C to 106 °C. Full article

Discotic (disk-shaped) molecules or molecular aggregates may form, within a certain temperature range, partially ordered phases, known as discotic liquid crystals, which have been extensively studied in the recent past. On the one hand, this interest was prompted by the fact that they represent models for testing energy and charge transport theories in organic materials. However, their long-range self-assembling properties, potential low cost, ease of processability with a variety of solvents and the relative ease of tailoring their properties via chemical synthesis, drove the attention of researchers also towards the exploitation of their semiconducting properties in organic electronic devices. This review covers recent research on the charge transport properties of discotic mesophases, starting with an introduction to their phase structure, followed by an overview of the models used to describe charge mobility in organic substances in general and in these systems in particular, and by the description of the techniques most commonly used to measure their charge mobility. The reader already familiar or not interested in such details can easily skip these sections and refer to the core section of this work, focusing on the most recent and significant results regarding charge mobility in discotic liquid crystals. Full article

Tristriazolotriazines (TTTs) with a threefold alkoxyphenyl substitution were prepared and studied by DSC, polarized optical microscopy (POM) and X-ray scattering. Six pentyloxy chains are sufficient to induce liquid-crystalline behavior in these star-shaped compounds. Thermotropic properties of TTTs with varying substitution patterns and a periphery of linear chains of different lengths, branching in the chain and swallow-tails, are compared. Generally, these disks display broad and stable thermotropic mesophases, with the tangential TTT being superior to the radial isomer. The structure–property relationships of the number of alkyl chains, their position, length and structure were studied. Full article

In liquid crystal applications, boundary conditions are essential to ensuring suitable bulk molecular orientation and a deterministic response to external fields. Be it confinement to a droplet or a shell, a glass plate, or an interface with air or another liquid, proper surface alignment must be ensured—mechanically by rubbing, by chemical treatment that adds a layer of aligning molecules, by using photoalignment or even by leaving the surface untreated, using the intrinsic properties of the substrate itself. The anchoring can be classified as unidirectional (perpendicular homeotropic, or at oblique angles), or degenerate (planar or pre-tilted). However, if both substances at the interface are anisotropic, more diverse behaviour is expected. Here, we present a numerical simulation of a nematic droplet in a nematic host, and investigate behaviour of the director field and defects at the interface for different interfacial couplings. Finally, we compare the simulations to experimental images of discotic droplets in a calamitic nematic host. Full article

The review summarizes the literature data and the authors’ own research results on the application of liquid crystals in tribology. It has been shown that both thermotropic (calamitic, discotic, cholesteric) and lyotropic (surfactants, chromonics) mesogens as tribological additives are able to optimize the properties of lubricating compositions when introduced even at low concentrations to oils and greases. A wide possibility of varying the chemical structure of mesogens and studying the relationship between their structure and tribological properties can be used for the desired (programmed) change of the quality of tribotechnical processes. The synergism of the combined use of mesogenic esters of cholesterol and carbon nanostructures as additives in improving tribological properties has been established. The use of synthetic lubricants in biological systems still requires further research as the experimental results obtained on models of joint prostheses in vitro conditions are significantly worse than the results obtained in vivo. Considering the annual loss of billions of US dollars worldwide due to the low efficiency of friction processes in the industry and the resulting wear, liquid crystals and the systems based on them can be the most effective way to optimize these processes. The present review will be useful for researchers and industrialists. Full article

The ionic conductivity of an electrolyte is represented by a product of carrier density, charge (electric), and ionic mobility. The overall goal of this study was to provide an insight into the influence of lithium ion conductivity and dynamic when a continuous discotic liquid crystal (DLC) matrix of hexaazatrinapthylene-polyether, HATN-TEG-1, is doped with a small amount of polyethylene oxide (PEO, 5% of MW 8000). The favorable non-covalent interactions between PEO and the DLC triethylene glycol side-chains is supported by the maintenance of the mesophase. The lithium ionic conductivity of HATN-TEG-1 was found to be 1.1 × 10⁻⁶ S cm⁻¹, which is better than the corresponding HATN-TEG-1-5%PEO-8000 with a value of 6.06 × 10⁻⁷ S cm⁻¹. These results are further supported by the dynamics of the lithium ions in HATN-TEG-1 and HATN-TEG-1-5%PEO-8000 as characterized by ⁷Li, and ¹H NMR spin-lattice relaxation time and self-diffusion coefficient measurements. Though the additional PEO was found to increase the ion carriers, the significant lowering of the ionic conductivity may be attributed to the more pronounced decrease of the mobility of the ionic part when the HATN-TEG-1 matrix is dispersed with PEO. This finding indicates that the doping of 5% PEO onto the matrix of HATN-TEG-1 DLC has an adverse effect on both its diffusion rate and ion conductivity. Full article

The Li⁺- and K⁺-complexes of new discotic mesogens, where two n-alkoxy-substituted triphenylene cores are connected by a central crown ether (12-crown-4 and 18-crown-6), provide interesting structural and electronic properties. The inter- and intra-columnar structure was investigated by small and wide angle X-ray scattering. The electronic and ionic transports were studied by temperature dependent photoconductivity and impedance spectroscopy, respectively. Besides a strong increase of the stability and the width of the columnar phases the presence of soft anions (iodide, thiocyanate, tetrafluoroborate) leads to an improved intra-columnar order. The hereby shortened stacking-distance of the triphenylene cores leads to a significant increase of the photoconductivity in the columnar mesophase. Furthermore, the ionic conductivity of the new materials was investigated on macroscopically aligned thin films. The existence of channels for fast cation transport formed by the stacked crown ether moieties in the centre of each column can be excluded. The cations are coordinated strongly and therefore contributing only little to the conductivity. The ionic conductivity is dominated by the anisotropic migration of the non-coordinated anions through the liquid, like side chains favouring the propagation parallel to the columns. Iodide migrates about 20 times faster than thiocyanate and 100 times faster than tetrafluoroborate. Full article

This article primarily summarizes recent advancement in the field of discotic liquid crystal (DLC) nanocomposites. Discotic liquid crystals are nanostructured materials, usually 2 to 6 nm size and have been recognized as organic semiconducting materials. Recently, it has been observed that the dispersion of small concentration of various functionalized zero-, one- and two-dimensional nanomaterials in the supramolecular order of mesophases of DLCs imparts negligible impact on liquid crystalline properties but enhances their thermal, supramolecular and electronic properties. Synthesis, characterization and dispersion of various nanoparticles in different discotics are presented. Full article