A new class of bent‐shaped mesogens exhibiting unusual mesophase behaviour

Examples of a new class of bent‐core compounds are presented, the central fragment of which consists of a benzoyl derivative of a secondary cyclic amine. The mesophase behaviour has been studied by differential scanning calorimetry, polarizing optical microscopy, X‐ray diffraction and electro‐optical measurements. It was found that the five‐ring compounds form smectic CP or B₁ phases which are typical for bent‐core mesogens. The six‐ring compounds exhibit, in some cases, only conventional non‐polar smectic phases; in other cases non‐polar smectic phases as well as banana phases are seen. Of particular interest is the occurrence of a switchable uniaxial semectic A‐like phase with an antiferroelectric structure.     

Bent‐core mesogens based on semi‐flexible dicyclohexylmethane spacers

New, bent‐core mesogens are described in which the core of the molecule is a semiflexible, di(4‐aminocyclohexyl)methane spacer. The compounds show nematic, columnar nematic and columnar phases as shown by a combination of X‐ray diffraction and optical microscopy. The potential of these new mesogens as biaxial nematic candidates is considered.     

Enantiotropic Nematics From Cross‐Like 1,2,4,5‐Tetrakis(4′‐alkyl‐4‐ethynylbiphenyl)benzenes and Their Biaxiality Studies

The theoretically predicted optimum length/breadth/width ratio for maximizing shape biaxiality was investigated experimentally by the facile and successful synthesis of cross‐shaped compound 3 , which showed enantiomeric nematic phase behavior. This cross‐like core structure could alternatively be viewed as two fused V‐shaped mesogens, which have recently immerged as a new direction in biaxial nematic research, at the bending tips that can act as a new structure for biaxial investigations. Whilst the thermal analysis data of compound 3 did not meet the expected theoretical values for biaxial nematics, surface‐induced biaxiality was evidenced by optical studies. Cluster‐size analysis within the nematic phase of compound 3 revealed the formation of meta‐cybotactic nematics, which approached the cluster sizes of cybotactic nematics. The split small‐angle 2D X‐ray diffraction patterns of magnetic‐field‐aligned samples indicated that the nematic phase was composed of small smectic C‐like clusters with the tilting of molecules within the clusters. The wide‐temperature‐range enantiomeric nematic phase of cross‐like compound 3 enabled the molecular skeleton to serve as an alternative skeleton to bent‐rod mesogens, which exhibited nematic phases with the potential competition of transitions to higher‐order liquid‐crystalline phases and crystallization, for future biaxial investigations.     

Dependence of Mesomorphic Behaviour of Methylene‐Linked Dimers and the Stability of the NTB/NX Phase upon Choice of Mesogenic Units and Terminal Chain Length

Twelve symmetrical dimeric materials consisting of a nonamethylene (C9) spacer and either phenyl 4‐(4′‐alkylphenyl)benzoate, phenyl 4‐(4′‐alkylcyclohexyl)benzoate or phenyl 4‐(4′‐alkylbicyclohexyl)carboxylate mesogenic units were prepared and their mesogenic behaviour characterised by POM, DSC and XRD. All of the materials exhibited nematic phases with clearing points in excess of 200 °C. Four compounds were found to exhibit the twist‐bend nematic phase, with one material exhibiting a transition from the N_TB phase into an anticlinic smectic ‘X’ phase. Across all three series of compounds the length of terminal chain is seen to dictate, to some degree, the type of mesophase formed: shorter terminal chains favour nematic and N_TB mesophases, whereas longer terminal aliphatic chains were found to promote smectic phases.     

Synthesis and Characterization of Achiral Bent‐Core Liquid Crystalline Molecules Containing Salicylaldimine‐Based with a Wide Temperature Range of SmCP Phase

The design and synthesis of a series bent‐core materials base on a 3,4′‐biphenyldiol central core containing salicylaldimine‐based and two terminal tetradecyloxy tails are reported. In addition, the effects of lateral substituents (R = F and Cl) at the biphenyl core into 3′‐position are examined. These substituents have a strong influence in reducing the clearing temperatures and increasing temperature range of SmCP phase. Upon cooling process the isotropic liquid, compound SB‐Cl exhibits the lowest clearing transition temperature of 180°C and the widest SmCP phase range of 129°C. The mesophase behaviour were investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and electro‐optical (EO) measurements in the mesophase temperature range.     

Ionic Bent Shape Ternary Facial Amphiphiles

Novel bent shape tenary facial amphiphilic imidazolium ILC which consist of a π‐conjugated bent aromatic cores (2,5‐dithiophenylethynyl phenyl bent core), two terminal poliphilic alkyl chains and lateral n‐alky chain terminated by an imidazolium bromide unit were synthesized by using Kumada and Sonogashira coupling reactions as key steps and both their thermotropic and lyotropic mesophase behaviors were studied by POM, DSC and XRD. Columnar phases were found in these compounds, a hexagonal cylinder model with core shell structure is supposed for the columnar phase formed by compound I/8 . Our study may provide a new strategy for designing new LC functional material.     

Not Only Columns: High Hole Mobility in a Discotic Nematic Mesophase Formed by Metal‐Containing Porphyrin‐Core Dendrimers

We report a new family of multifunctional liquid‐crystalline porphyrin‐core dendrimers that have coumarin functional groups around the porphyrin core. Porphyrin metalation strongly affects the photophysical properties, and therefore Zn^II and Cu^II derivatives have also been prepared. All the synthesized dendrimers form a nematic discotic mesophase. Their high tendency for homeotropic alignment makes these dendrimers excellent candidates for device applications, owing to their easy processability, spontaneous alignment between electrodes, and self‐healing of defects because of their dynamic nature. The charge mobility values of these materials are the highest ever reported for a nematic discotic phase. Moreover, these values are similar to the highest values reported for ordered columnar mesophases, and this shows that a supramolecular organization in columns is not necessary to achieve high charge mobility.     

非传统型液晶分子设计与工程研究进展

从液晶基元连接方式、液晶分子拓扑结构以及凝聚态自组织方式等方面扼要介绍和评述了非传统型液晶分子设计与工程研究进展,并重点介绍了可望引起液晶显示技术革命的双轴向列相香蕉形液晶研究的突破性工作,展望了非传统型液晶分子设计和复杂自组织超分子液晶领域今后的发展方向。     

Helical Nano‐crystallite (HNC) Phases: Chirality Synchronization of Achiral Bent‐Core Mesogens in a New Type of Dark Conglomerates

Spontaneous generation of macroscopic homochirality in soft matter systems by self‐assembly of exclusively achiral molecules under achiral conditions is a challenging task with relevance for fundamental scientific research and technological applications. Dark conglomerate phases (DC phases), being optically isotropic mesophases composed of conglomerates of macroscopic chiral domains and formed by some non‐chiral bent‐core mesogens, represent such a case. Here we report two new series of non‐symmetric bent‐core molecules capable of forming a new type of mirror symmetry broken DC phases. In the synthesized molecules, a bent 4‐bromoresorcinol core is connected to a phenyl benzoate wing and an azobenzene wing with or without additional peripheral fluorine substitution. The self‐assembly was investigated by DSC, polarizing microscopy, electro‐optical studies and XRD. Chiral and apparently achiral DC phases were observed besides distinct types of lamellar liquid crystalline phases with different degree of polar order, allowing the investigation of the transition from smectic to DC phases. This indicates a process in which increased packing density at first gives rise to restricted rotation and thus to growing polar order, which then leads to chirality synchronization, layer frustration and nano‐scale crystallization. Topological constraints arising from the twisted packing of helical conformers in lamellar crystals is proposed to lead to amorphous solids composed of helical nano‐crystallites with short coherence length (HNC phases). This is considered as a third major type of DC phases, distinct from the previously known liquid crystalline sponge phases and the helical nano‐filament phases (HNF phases). Guidelines for the molecular design of new materials capable of self‐assembly into these three types of DC phases are proposed.     

Chiral and orientationally ordered fluid mesophases formed by oxadiazole bisaniline based achiral bent mesogens

Development of new liquid crystalline materials exhibiting interesting properties and phases continues to be an enabling enterprise in the forward march of their successful display and non-display applications. The design and synthesis of a homologous series of liquid crystalline bent-core compounds derived from the oxadiazole bisaniline moiety and the phase behavior of three members of the series that exhibit nematic, smectic C, and dark conglomerate phases is reported. The liquid crystalline phases exhibited by these mesogens are characterized using polarized optical microscopy, differential scanning calorimetry and x-ray scattering techniques. All three homologs prepared exhibit the nematic phase. Interestingly, the homolog with short hexyl terminal chains exhibits only the nematic phase that is stable over a very broad, nearly 100 K wide, temperature range. The compound with terminal octyl chains shows the chiral dark conglomerate phase below the nematic phase despite the bent molecules being achiral. The homolog with dodecyl alkyl chains is found to possess the smectic-C and two additional lamellar phases besides the nematic phase. These compounds enrich the library of achiral bent-core materials capable of exhibiting chiral and nematic phases.     

Synthesis, mesomorphism, and unusual magnetic behaviour of lanthanide complexes with perfluorinated counterions

Lanthanide complexes of the Schiff base ligand 4-dodecyloxy-N-hexadecyl-2-hydroxybenzaldimine and with perfluorinated alkyl sulfate counterions were synthesised. All of the metal complexes show a smectic A mesophase. The viscosity of this mesophase is much lower than that of analogous compounds with nitrate or alkyl sulfate counterions. The behaviour of these new highly anisotropic molecular magnetic materials was studied using high-temperature X-ray measurements in an external magnetic field and temperature-dependent magnetic susceptibility measurements. The mu(eff)-versus-temperature curve is more comparable with those expected for nematic phases than for smectic phases. The luminescence spectrum of a EuIII compound shows that the values of the second rank crystal field parameters are very large. The huge magnetic anisotropy can be related to this strong crystal-field perturbation.     

Liquid crystalline materials with complex mesophase morphologies

Liquid crystals, which combine order and mobility on a molecular and supramolecular level are increasingly accepted as a fourth state of matter. Besides the well-established nematic, smectic and columnar mesophases, more complex mesophase morphologies attracted increasing interest during the recent years. These are bicontinuous and discontinuous cubic mesophases and other two- and three-dimensionally ordered intermediate phases, superstructures induced by molecular chirality or by polar order of bent core molecules, novel biaxial smectic phases, and novel mesophase morphologies of polyphilic block molecules and dendrimers.     

New thermotropic liquid crystals derived from thiophenes

Properties of new homologous series of low molecular mass thermotropic liquid crystals containing non-linear mesogenic cores, 2,5-thiophene (T) and 2,2'-bithio-phene (BT), are presented for the purpose of refining molecular structural prerequisities for liquid crystallinity. Herein we focus on the effect of core linearity on mesophase stability. The bis(p-alkoxyphenyl) dicarboxylate derivatives containing the bent T and kinked BT central units are found to form enantiotropic liquid crystal phases with nematic and smectic polymorphism, depending on the length of their terminal chains. All members of the non-linear T and BT homologous series have narrower mesomorphic temperature ranges than the corresponding compounds with linear central units (p-phenylene and 4, 4'-biphenyl); liquid crystallinity is not found in the analogous m-phenylene derivatives. This finding is consonant with the established principles of prolate mesogen structural requirements, i.e. core linearity is closely related to liquid crystal phase formation and deviation from core linearity lowers mesophase stability. The results of this study indicate that the 2,5-thiophene and 2,2'-bithiophene moieties with non-linear structures are viable mesogenic core units and may be substituted for p-phenylene units in conventional liquid crystal molecules. Moreover, these moieties should be particularly useful for modifying the transition temperatures of liquid-crystalline polymers.     

Observation of disordered mesomorphism in three-ring-based highly polar bent-core molecules: design,synthesis and characterisation

Research on low-temperature polar bent-core nematogens having lower molecular weight has gathered appreciable momentum by virtue of their significance in potential applications. However, the lack of availability and easy-to-perform synthesis processes appears to be the bottleneck towards their fabrication and thereby limiting their possible device applications. Hence, we have designed a new class of achiral symmetrical three-ring-based-bent shaped molecules incorporating an imine and ester linkage at the molecular bend with highly polar nitro/cyano terminal moiety exhibiting low-temperature nematic mesmorphism. The occurrence of disordered nematic mesomorphism has been confirmed by optical texture, differential scanning calorimetry scan and X-ray diffraction measurement. Dielectric spectroscopy and electro-optical investigation has also been carried out intending towards the potential applicability of the materials. Density functional theory analyses at the molecular level provide valuable information regarding the formation of the nematic mesophase and various parameters of the molecular spatial arrangement. Polarising optical microscopy study reveals the easy of alignment of these types of polar bent-core materials upon glass surface suitable for liquid-crystal-based sensing applications. Formation of mesophase with such a small bent molecule is rather difficult but we have successfully demonstrated the existence of disordered nematic mesomorphism at relatively low temperature.     

A Twist‐Bend Nematic Phase Driven by Hydrogen Bonding

The liquid crystalline phase behavior of 4‐[6‐(4′‐cyanobiphenyl‐4‐yl)hexyloxy]benzoic acid (CB6OBA) and 4‐[5‐(4′‐cyanobiphenyl‐4‐yloxy)pentyloxy]benzoic acid (CBO5OBA) is described. Both acids show an enantiotropic nematic phase attributed to the formation of supramolecular complexes by hydrogen bonding between the benzoic acid units. In addition, CB6OBA provides the first example of hydrogen bonding driving the formation of the twist‐bend nematic phase. The observation of the twist‐bend nematic phase for CB6OBA, but not CBO5OBA, is attributed to the more bent molecular shape of the complexes formed by the former, reinforcing the view that shape is a key factor in stabilizing this new phase. Temperature‐dependent FTIR spectroscopy reveals differences in hydrogen bonding between the two nematic phases shown by CB6OBA which suggest that the open hydrogen‐bonded complexes may play an important role in stabilizing the helical arrangement found in the twist‐bend nematic phase.     

Pentaerythritol Derived Tetrapode Exhibiting a Nematic-Like Mesophase at Ambient Temperatures

The nematic liquid-crystalline phase exhibits average orientational order, with no positional organisation. So-called modulated nematic phases exhibit this same orientational order with an additional spatially periodic modulation of the nematic director, the most common of which is the twist-bend nematic phase. We report a pentaerythritol derived tetrapode which exhibits a nematic-like mesophase at ambient temperature, and we denote this new mesophase ‘N_X’ to indicate a nematic phase of unknown structure. X-ray scattering experiments refute the possibility of positional order, yet optical textures are consistent with a periodic structure. We suggest that the mesophase exhibited by this material is a new type of nematic-like mesophase with some form of modulated structure. We find the N_X phase to exhibit an electrooptic response consistent with a nematic-like phase.     

A Nanohelicoidal Nematic Liquid Crystal Formed by a Non‐Linear Duplexed Hexamer

The twist‐bend modulated nematic liquid‐crystal phase exhibits formation of a nanometre‐scale helical pitch in a fluid and spontaneous breaking of mirror symmetry, leading to a quasi‐fluid state composed of chiral domains despite being composed of achiral materials. This phase was only observed for materials with two or more mesogenic units, the manner of attachment between which is always linear. Non‐linear oligomers with a H‐shaped hexamesogen are now found to exhibit both nematic and twist‐bend modulated nematic phases. This shatters the assumption that a linear sequence of mesogenic units is a prerequisite for this phase, and points to this state of matter being exhibited by a wider range of self‐assembling structures than was previously envisaged. These results support the double helix model of the TB phase as opposed to the simple heliconical model. This new class of materials could act as low‐molecular‐weight surrogates for cross‐linked liquid‐crystalline elastomers.     

Synthesis of Fluorinated Bent‐Core Mesogens (BCMs) Containing the 1,2,4‐Oxadiazole Ring

New fluorinated bent‐core mesogens containing the 1,2,4‐oxadiazole or 1,2,4‐triazole nucleus have been synthesized taking advantage of the ANRORC ( A ddition of N ucleophile, R ing‐ O pening, R ing‐ C losure) reactivity of 5‐perfluoroalkyl‐1,2,4‐oxadiazoles. Physical state changes of the obtained compounds were characterized through DSC, POM, and SAXS. Besides the formation of a smectic mesophase, a novel behavior as organic molecular glass was evidenced for some 1,2,4‐oxadiazole derivatives.     

A Twist‐Bend Nematic (NTB) Phase of Chiral Materials

New chiral dimers consisting of a rod‐like and cholesterol mesogenic units are reported to form a chiral twist‐bend nematic phase (N_TB*) with heliconical structure. The compressibility of the N_TB phase made of bent dimers was found to be as large as in smectic phases, which is consistent with the nanoperiodic structure of the N_TB phase. The atomic force microscopy observations in chiral bent dimers revealed a periodicity of about 50 nm, which is significantly larger than the one reported previously for non‐chiral compounds (ca. 10 nm).     

Apolar Bimesogens and the Incidence of the Twist–Bend Nematic Phase

The nematic twist–bend phase (N_TB) was, until recently, only observed for polar mesogenic dimers, trimers or bent‐core compounds. In this article, we report a comprehensive study on novel apolar materials that also exhibit N_TB phases. The N_TB phase was observed for materials containing phenyl, cyclohexyl or bicyclooctyl rings in their rigid‐core units. However, for materials with long (>C7) terminal chains or mesogenic core units comprising three ring units, the N_TB phase was not observed and instead the materials exhibited smectic phases. One compound was found to exhibit a transition from the N_TB phase to an anticlinic smectic C phase; this is the first example of this polymorphism. Incorporation of lateral substitution with respect to the central core unit led to reductions in transition temperatures; however, the N_TB phase was still found to occur. Conversely, utilising branched terminal groups rendered the materials non‐mesogenic. Overall, it appears that it is the gross molecular topology that drives the incidence of the N_TB phase rather than simple dipolar considerations. Furthermore, dimers lacking any polar groups, which were prepared to test this hypothesis, were found to be non mesogenic, indicating that at the extremes of polarity these effects can dominate over topology.