Mesogenic Units Research Articles

Dynamically Switchable Global Chirality in Racemic Polymer Systems

Any polymers composed of racemic segments are obviously optically inactive and lack any chiroptical applications. Here, we present an intriguing method for precisely generating global chirality in racemic copolymer assemblies without any external asymmetrical intervention via step‐wise polymerization‐induced chiral self‐assembly (PICSA). Global supramolecular chirality of the nanoaggregates could be dynamically switched by the two diametrically opposed chiral conflict effects: “first come, first serve” effect and “late‐comer lives above” effect, which can be controlled by the precisely specified the number and sequence of enantiomeric segments. Significantly, the supramolecular stacking manners of the racemic mesogenic building units as well as the liquid crystallinity of the solvophobic core play a crucial role for the chiral communication pathway of enantiomeric mesogens. Furthermore, such switchable global chirality in racemic polymers is broadly applicable and well regulable. We propose that this research may challenge the notion that racemic systems lack optical activity while highlighting their potential applications in functional racemic polymer materials and providing insights into the evolution of racemates towards homochirality on early Earth.

Dynamically Switchable Global Chiralityin Racemic Polymer Systems.

Any polymers composed of racemic segments are obviously optically inactive and lack any chiroptical applications. Here, we present an intriguing method for precisely generating global chirality in racemic copolymer assemblies without any external asymmetrical intervention via step-wise polymerization-induced chiral self-assembly (PICSA). Global supramolecular chirality of the nanoaggregates could be dynamically switched by the two diametrically opposed chiral conflict effects: "first come, first serve" effect and "late-comer lives above" effect, which can be controlled by the precisely specified the number and sequence of enantiomeric segments. Significantly, the supramolecular stacking manners of the racemic mesogenic building units as well as the liquid crystallinity of the solvophobic core play a crucial role for the chiral communication pathway of enantiomeric mesogens. Furthermore, such switchable global chirality in racemic polymers is broadly applicable and well regulable. We propose that this research may challenge the notion that racemic systems lack optical activity while highlighting their potential applications in functional racemic polymer materials and providing insights into the evolution of racemates towards homochirality on early Earth.

Effect of mesogenic linkages on two novel aromatic series-based liquid crystals: synthesis, theoretical and comparative studies

ABSTRACT Two novel groups of rod-like homologue molecules, one group (group A) having benzothiazole-aromatic mesogenic units and the other (group B) with only aromatic mesogenic units, were designed and synthesised. Both groups (compounds A and B) involve azomethine (−CH=N−), ester (−COO−), azo (−N=N−) and amide (−NH−CO−) linking groups at the different positions in their molecular structures. The structures of the synthesised compounds were elucidated using different analytical techniques (1H, 13C NMR, FT−IR, mass spectra and melting points). In order to verify the influence of the central linkages and their positions on physicothermal and mesomorphic properties, different types of linking groups including −CH=N−, −COO-, −N=N− and −NH−CO− were analytically and thermally investigated. Thermal analyses and mesomorphic properties of both series are discussed in terms of the linkages nature, comprising geometrical structure, interactions polarisability, subtle change in shape and their effective positions. The results revealed that the synthesised compounds (groups A and B) showed the only enantiotropic nematic mesophase in certain temperature regions except compounds A4 and A6. The change of the type linkages and their positions in some compounds (groups A and B) was theoretically investigated to verify if the theoretical calculations show an agreement with the experimental findings.

New Molecularly Flexible Self-Assembling Benzothiadiazole Derivatives: Mesomorphism And DFT Investigations

In the present study, we have synthesized symmetric/unsymmetrical BTD embedded self-assembling molecules and investigated for their mesomorphic properties. Two symmetrical series (BTDK-(2-18) and BTDC-(4-18)) comprises benzothiadiazole moiety as a central core unit which is connected to two different systematically varied end-groups, alkoxy ester and alkoxy coumaryl unit connected through ether and imine linkages. On the other hand, the asymmetric molecules have an alkoxy chalconyl unit at one end and a formyl group at the other. It was observed that, the mesomorphism is completely depends on the molecular flexibility. New molecules revealed mesomorphic behaviour with N (nematic), SmA (smectic-A) and SmC (smectic-C) mesophase with high thermal stability and greater range. Changes in mesogenic units (alkoxy ester & alkoxy coumaryl unit) and the impact of altering the alkoxy chain at both ends have been investigated. Interesting evaluation has been carried out on the molecular flexibility which resulted in different mesomorphic behaviour of molecules under study. Furthermore, the experimentally established values of the mesophase thermal stability (Tc) and mesophase temperature ranges (ΔTSmA, ΔTSmC, and ΔTN), as well as the type of the mesophase, were related to the calculated quantum chemical parameters (Frontier molecular orbitals (FMOs), Aspect Ratio, Polarizability, dipole moment, molecular and electrostatic potential (MEP)) that were obtained by using the DFT method of the investigated compounds.

Smectogenic asymmetric naphthalene derived chalcones: Self-assembling behaviour and DFT studies

A series of new naphthalene derived asymmetric benzoates incorporating chalcone unit NPCH-(2–16) have been synthesized and investigated for their self-assembling behaviour. The naphthalene end of molecules linked to decyloxy long chain whereas the other end possess systematically substituted chalcone unit connected through ester and imine linking mesogenic units. New molecules have been found to exhibit smectogenic behaviour investigated by POM (polarising optical microscopy) and DSC (differential scaling calorimetry) investigations. Early members (C1 and C7) showed enantiotropic smectic-A (SmA) behaviour, whereas molecules with C8 and C10 showed enantiotropic SmA along with monotropic smectic-C (SmC) also during cooling scans. All afterwards molecules (C12-C16) with longer alkyl chains tend to exhibit enantiotropic SmC mesophase. For one of the representative compounds, the presence of mesophase was confirmed by VT-XRD (variable temperature X-ray-crystallography) analysis. Additionally, the density functional theory (DFT) method has been applied to provide an in-depth analysis of the relationship between the computed structural (length, aspect ratio) and electronic (dipole moment, polarizability) variables and the mesomorphic behaviour of investigated compounds.

Preparation of polyimide films with ultralow dielectric loss at high frequency by reducing intermolecular friction

Due to the rapid development of high frequency and high rate communication technology, polyimide (PI) films with ultra-low dielectric loss (Df) at high frequency, excellent thermal and mechanical properties are urgently needed. A series of PI films with ultra-low Df were prepared by introducing different mesogen units. Among them, one novel PI film with biphenyl liquid-crystal-like units (BAHQ-TFMB) achieve a recorded low Df of 0.00169 (10 GHz) which surpasses previous studies on pure PI bulk films. Importantly, the high degree of collinearity of the friction work (Wf) and Df of PI films (Pearson's r = 0.992) was confirmed, which indicate that Wf among PI macromolecules plays an important role in determining Df of PI films. To reveal underlying reason for reducing the Wf and Df of PI films, the contribution of the degree of orientation and crystallinity of PI films with or without liquid-crystal-like structures were comparative studied. Through a two-dimensional orientation determinant, it is found that increasing the crystallinity of liquid-crystal-like PI films is the main contribution to reducing Wf and corresponding Df of PI films while the orientation of PI films seems to have weak effect. Moreover, BAHQ-TFMB PI film exhibits excellent mechanical properties. The tensile strengths is 145.5 ± 12.0 MPa and Young's moduli is 4.76 ± 0.28 GPa.

Insights into the electronic structure and interaction energies of 4-ethoxy-N-(4-ethoxy-2-hydoxybenzylidene)benzohydrazide

The molecule 4-ethoxy-N-(4-ethoxy-2-hydroxybenzylidene)benzohydrazide (4EHB) is characterized by a rigid aroylhydrazone core, acting as a mesogenic unit, and a flexible chain at its terminal end. The aroylhydrazone core comprises two aromatic rings linked by connecting groups, resulting in moderate size and elongation of the molecule. Variations in the positions and orientations of elongated molecules give rise to different mesogenic phases such as Nematic, Smectic, and Hexatic Smectic. The mesogenic behavior of aroylhydrazone-based materials is governed by various non-covalent interactions. In this study, molecular geometry optimization, analysis of HOMO-LUMO orbitals, and MEP surfaces of individual and pairs of 4EHB molecules were conducted using the Density functional B3LYP technique with the basis set 6-31G**. Intermolecular interaction energies between pairs of 4EHB molecules are evaluated using the technique M06-2X/6-311G** in stacking, terminal, and side-to-side (in-plane) configurations. Basis set superposition error (BSSE) is corrected using counterpoise method and interaction energy(I.E.) is decomposed in different components using SAPT0 method at level 6-311G**, which provided insights into the mesogenic behavior of the system.

Current Trends in Liquid Crystal Polymers and Their Applications: A Review

Liquid crystal polymers (LCPs) are now highly focused by researchers due to their improved thermal properties, mechanical strength, excellent dielectric strength, resistance to solvents, better dimensional stability, and gas barrier properties. LCPs can be used in valuable widespread applications such as energy storage, high-performance polymer fibers, actuators, information technologies, surface modification, shape memory materials, data storage, fiber optics, the medical field, electrical or electronics devices, aircraft, chemical, domestic equipment, ultra-high-strength fibers, biosensing, advanced communication systems, satellite systems, biosensing, bio-oscillators, and bioprocess monitoring. LCPs can self-assemble into different liquid crystalline phases like nematic, cholesteric, smectic, and columnar phases. The self-assembling structures of LCPs can be affected by the chemical and structural structures of the backbone of the polymeric material, nearby alkyl tails, mesogenic units, flexible spacers, etc. Depending on the mesogenic units in their molecular architecture, LCPs are basically classified into various categories, such as crosslinked, main chain, and sidechain. Again, they are also classified as cholesteric, nematic, and smectic mesophases. This paper provides a fundamental understanding, an informative overview, and details of structural aspects, properties, classification, commercial aspects, and applications of LCPs.

Comparative Study of the Optical and Dielectric Anisotropy of a Difluoroterphenyl Dimer and Trimer Forming Two Nematic Phases.

We present a comparative study of the optical and dielectric anisotropy of a laterally fluorinated liquid crystal dimer and its homologous trimer, both exhibiting two nematic phases. In the high-temperature nematic phase, both oligomers exhibit positive optical anisotropy with similar magnitude, which, however, is lower in comparison with the optical anisotropy of the monomer. In the same temperature range, the dielectric permittivity along and perpendicular to the nematic director, measured on magnetically aligned samples, reveals negative dielectric anisotropy for both oligomers, which saturates as the temperature approaches the N-N phase transition temperature. Comparison of the dielectric anisotropies of the oligomers with the corresponding anisotropy of the monomer indicates a systematic variation of its magnitude with the number of the linked mesogenic units. Results are compared with the corresponding anisotropies of the cyanobiphenyl dimers, the archetypal compounds with two nematic phases, and are discussed in terms of the dipolar structure of the mesogens and the dipolar correlations in their nematic phases.

Liquid Crystal Dimers and the Twist-Bend Phases: Non-Symmetric Dimers Consisting of Mesogenic Units of Differing Lengths.

The syntheses and characterisation of the 4-[{[4-({n-[4-(4-cyanophenyl)phenyl]-n-yl}oxy)phenyl]-methylidene}amino]phenyl-4-alkoxybenzoates (CBnOIBeOm) are reported with n=8 and 10 and m=1-10. The two series display fascinating liquid crystal polymorphism. All twenty reported homologues display an enantiotropic nematic (N) phase at high temperature. When the length of the spacer (n) is greater than that of the terminal chain (m), the twist-bend nematic (NTB) phase is observed at temperatures below the N phase. As the length of the terminal chain is increased and extends beyond the length of the spacer up to three smectic phases are observed on cooling the N phase. One of these smectic phases has been assigned as the rare twist-bend smectic C subphase, the SmCTB-α phase. In all the smectic phases, a monolayer packing arrangement is seen, and this is attributed to the anti-parallel associations of the like mesogenic units.

A design approach to obtaining highly polar liquid crystal dimers

ABSTRACT The synthesis and characterisation of 10 members of the [4[(E)-[4-[4-[ω-(4-cyanophenyl)phenoxy]alkyloxy]-3-nitrophenyl]methylideneamino]phenyl] 2,4-dimethoxybenzoates is reported in which the number of methylene units in the flexible spacer is increased from three to twelve. The mesogenic units are based on cyanobiphenyl and 3-nitrobenzylideneaniline benzoate and linked by the spacer such that their dipoles are parallel giving rise to a large longitudinal dipole moment. All 10 members of the series show a nematic phase, and the nematic-isotropic transition temperatures, TNI, and associated entropy changes show a strong dependence on the length and parity of the spacer. This behaviour is attributed to the average shapes of the molecules and their flexibility. The heptyl member was further characterised using dielectric spectroscopy revealing a high value of dielectric permittivity reflecting the large dipole moment of the molecules and possibly indicating local short-range ferroelectric order. The synthesis and characterisation of two members of the [4[(E)-[4-[4-[3-(ω-cyanophenyl)phenoxy]alkyloxy]-4-nitrophenyl]methylideneamino]phenyl] 2,4-dimethoxybenzoates are also described for which the difference in shape between odd and even members is reduced. Both dimers are exclusively nematogenic and the difference between TNI for the odd and even member is smaller reflecting the more similar molecular shapes. The potential for developing dimers that exhibit the ferroelectric nematic phase is discussed.

Statement of Retraction: Synthesis of Nanocrystalline Polycalix[4]amides Containing Mesogenic Triazole Units and Investigations of Their Thermo Physical Properties and Heavy Metal Sorption Behavior

Statement of Retraction: Synthesis of Nanocrystalline Polycalix[4]amides Containing Mesogenic Triazole Units and Investigations of Their Thermo Physical Properties and Heavy Metal Sorption Behavior

Terminal methylene biphenyl derived coumarin Schiff base-esters: Synthesis, mesomorphic behaviour and DFT investigations

In the present investigation new unsymmetrical coumarin-methylene biphenyl MBPCE-(2–16) mesogens were designed and synthesized. Methylene biphenyl end group at one end of molecules have been linked to the 7-alkyloxy substituted coumarin core through imine and ester mesogenic connecting units. The structures of new hybrids have been elucidated employing different analytical techniques including FT-IR, 1H NMR, 13C NMR, Mass & CHN elemental analysis. New molecules have been investigated for their mesomorphic behaviour using DSC (Measurement of transition temperature and enthalpy associated) and POM (Texture study) techniques and the existence of mesophase was established by VT-XRD analysis. Compounds with n = 2 (-OC2H5) to n = 7 (-OC7H15) chain length exhibited enantiotropic nematic mesophase with good thermal stability. As the chain length increases, compounds from n = 8 (-OC8H17) and n = 10 (-OC10H21) displayed enantiotropic nematic as well as smectic-A mesophase whereas compound with n = 12 (-OC12H25) showed only interdigitated SmA phase. Next two members of the series failed to show any mesomorphism. The commencement of SmA phase and disappearance of nematic could be attributed to more layer arrangement with increased van der waals interactions. The density functional theory (DFT) calculations were employed to complement the experimental results concerning the mesomorphic behaviour. Development of smectic phase could be due to the augmentation in the area of the intermolecular interaction which increases the degree of molecular packing. Conversely, it was discovered that higher polarizability leads to lower nematic thermal stability because it strengthens parallel intermolecular interactions, which promotes a higher degree of molecular order while reducing the development of lower-order nematic mesophase.

Novel liquid crystalline fluorene and fluorenone MIDA boronates: influence of alkyl vs alkoxy side chains on the mesomorphic properties

ABSTRACT To obtain novel boron liquid crystals, we successfully combined MIDA boronates with chromophoric fluorene and fluorenone mesogenic units and studied the influence of alkoxy versus alkyl side chains by differential scanning calorimetry (DSC), polarising optical microscopy (POM) and X-ray diffraction (XRD). The fluorenes showed broader temperature ranges of the SmA phase compared to their fluorenone counterparts. By replacing the alkoxy side chains with alkyl side chains, the mesophase ranges could be significantly enlarged and the thermal stability increased.

Advances in Liquid Crystal Epoxy: Molecular Structures, Thermal Conductivity, and Promising Applications in Thermal Management

Traditional heat conductive epoxy composites often fall short in meeting the escalating heat dissipation demands of large‐power, high‐frequency, and high‐voltage insulating packaging applications, due to the challenge of achieving high thermal conductivity (k), desirable dielectric performance, and robust thermomechanical properties simultaneously. Liquid crystal epoxy (LCE) emerges as a unique epoxy, exhibiting inherently high k achieved through the self‐assembly of mesogenic units into ordered structures. This characteristic enables liquid crystal epoxy to retain all the beneficial physical properties of pristine epoxy, while demonstrating a prominently enhanced k. As such, liquid crystal epoxy materials represent a promising solution for thermal management, with potential to tackle the critical issues and technical bottlenecks impeding the increasing miniaturization of microelectronic devices and electrical equipment. This article provides a comprehensive review on recent advances in liquid crystal epoxy, emphasizing the correlation between liquid crystal epoxy's microscopic arrangement, organized mesoscopic domain, k, and relevant physical properties. The impacts of LC units and curing agents on the development of ordered structure are discussed, alongside the consequent effects on the k, dielectric, thermal, and other properties. External processing factors such as temperature and pressure and their influence on the formation and organization of structured domains are also evaluated. Finally, potential applications that could benefit from the emergence of liquid crystal epoxy are reviewed.

Fabrication and Photothermal Actuation Performances of Electrospun Carbon Nanotube/Liquid Crystal Elastomer Blend Yarn Actuators.

Liquid crystal elastomers (LCEs) are a kind of polymer network that combines the entropic elasticity of polymer networks and the mesogenic unit by means of mild cross-linking. LCEs have been extensively investigated in various fields, including artificial muscles, actuators, and microrobots. However, LCEs are characterized by the poor mechanical properties of the light polymers themselves. In this study, we propose to prepare a carbon nanotube/liquid crystal elastomer (CNT/LCE) composite yarn by electrospinning technology and a two-step cross-linking strategy. The CNT/LCE composite yarn exhibits a reversible shrinkage ratio of nearly 70%, a tensile strength of 16.45 MPa, and a relatively sensitive response speed of ∼3 s, enabling a fast response by photothermal actuation. The research disclosed in this article may provide new insights for the development of artificial muscles and next-generation smart robots.

Modelling structure and ionic diffusion in a class of ionic liquid crystal-based solid electrolytes.

Next-generation high-efficiency Li-ion batteries require an electrolyte that is both safe and thermally stable. A possible choice for high performance all-solid-state Li-ion batteries is a liquid crystal, which possesses properties in-between crystalline solids and isotropic liquids. By employing molecular dynamics simulations together with various experimental techniques, we have designed and analyzed a novel liquid crystal electrolyte composed of rigid naphthalene-based moieties as mesogenic units, grafted to flexible alkyl chains of different lengths. We have synthesized novel highly ordered lamellar phase liquid crystal electrolytes at 99% purity and have evaluated the effect of alkyl chain length variation on ionic conduction. We find that the conductivity of the liquid crystal electrolytes is directly dependent on the extent of the nanochannels formed by molecule self-organization, which itself depends non-monotonously on the size of the alkyl chains. In addition, we show that the ion pair interaction between the anionic center of the liquid crystal molecules and the Li+ ions plays a crucial role in the overall conductivity. Based on our results, we suggest that further improvement of the ionic conductivity performance is possible, making this novel family of liquid crystal electrolytes a promising option for the design of entirely solid-state Li+ ion batteries.

A novel B,O,N-doped mesogen with narrowband MR-TADF emission.

Modification of an unsymmetric B,O,N-doped aromatic core with peripheral mesogenic units triggers self-assembly into a columnar hexagonal mesophase, which is stable between 22 and 144 °C. The columnar assembly is preserved in a glassy state below 22 °C. The B,O,N-doped mesogen displays narrowband sky-blue multiresonance thermally activated delayed fluorescence (MR-TADF) under diluted conditions and bright excimer emission in condensed phase. Our combined experimental and theoretical approach provides insight into the development of strongly aggregating liquid crystalline MR-TADF emitters.

Molecular Actuation of a Bistable Liquid‐Crystalline [c2]Daisy Chain Rotaxane

AbstractA bistable [c2]daisy chain rotaxane bearing two mesogenic units was synthesized, and its liquid crystal phase diagram was characterized. As a remarkable result, this study demonstrates that, depending on the contracted or extended state of its mechanical bond, the system can convert between an isotropic and a smectic A mesophase at constant temperature.

Effect of the Structure of Epoxy Monomers and Curing Agents: Toward Making Intrinsically Highly Thermally Conductive and Low-Dielectric Epoxy Resins.

The low intrinsic thermal conduction and high dielectric properties of epoxy resins have significantly limited their applications in electrical and electronic devices with high integration, high frequency, high power, and miniaturization. Herein, a liquid crystalline epoxy (LCE) monomer with a biphenyl mesogenic unit was first synthesized through an efficient one-step reaction. Subsequently, bisphenol AF (BPAF) containing low-polarizable -CF3 groups and 4,4'-diaminodiphenylmethane (DDM) were applied to cure the LCE and commercial diglycidyl ether of bisphenol A-type epoxy (E-51), respectively, to afford four kinds of epoxy resins with various intrinsic thermal conductivity and dielectricity values. Owing to the dual effect of microscopically stacking of mesogens and the contribution of fluorine to the formation of liquid crystallinity, ordered microstructures of the nematic liquid crystal phase were formed within the cross-linking network of LCE as confirmed by polarized optical microscopy and X-ray diffraction. Consequently, phonon scattering was suppressed, and the intrinsic thermal conductivity was improved considerably to 0.38 W/(m·K), nearly twice as high as that of E-51 cured with DDM (0.20 W/(m·K)). Additionally, the ordered microstructure and ultralow polar -CF3 groups within LCE cured with BPAF enabled the epoxy resin to exhibit a remarkably lower and stable dielectric constant (ε) and dielectric loss tangent (tan δ) over both low and high frequencies compared to E-51 cured with DDM. The ε decreased from 3.40 to 2.72 while the tan δ decreased from 0.044 to 0.038 at 10 GHz. This work presents a scalable and facile strategy for breaking the bottleneck of making epoxy resins simultaneously with high inherent thermal conduction and low dielectric performance.