Molecular design of flexible liquid crystal oligomers stabilising the chiral frustrated phases

ABSTRACT

Chirality induces structural frustration in liquid crystal systems, producing various kinds of chiral frustrated phases, for example, twist grain boundary (TGB) phases, blue phases (BPs) and dark conglomerate (DC) phases. Almost all molecules exhibiting these frustrated phases have a rigid shape. Especially, a bent–core unit is regarded as a key structure for BPs and DC phases. This paper describes that some flexible liquid crystal oligomers being far from a rigid bent–core molecule stabilise these phases. The LC oligomers have a supermolecular structure in which mesogenic units are connected via flexible spacers. By designing intermolecular interactions, they can exhibit various molecular packing structures in the liquid-crystalline phases as follows: chiral dimers inducing TGB phases, U-shaped and T-shaped oligomers stabilising BPs and achiral liquid crystal trimers exhibiting DC phases. I discuss how the designed liquid crystal oligomers produce the chiral frustrated phases.     

Trimeric and tetrameric liquid crystalline thiadiazole derivatives

Abstract

Novel liquid crystalline 2-phenyl-1,3,4-thiadiazole based oligomers with three and four rigid aromatic units linked by a flexible central unit have been investigated by polarizing microscopy. The synthesis of these compounds and the influence of structural variations on the mesomorphic properties are described. The combination of suitable mesogenic moieties with appropriate central units leads to oligomers which exhibit S_c phases.     

Reentrant 2D Nanostructured Liquid Crystals by Competition between Molecular Packing and Conformation: Potential Design for Multistep Switching of Ionic Conductivity

Reentrant phenomena in soft matter and biosystems have attracted considerable attention because their properties are closely related to high functionality. Here, we report a combined experimental and computational study on the self-assembly and reentrant behavior of a single-component thermotropic smectic liquid crystal toward the realization of dynamically functional materials. We have designed and synthesized a mesogenic molecule consisting of an alicyclic trans,trans-bicyclohexyl mesogen and a polar cyclic carbonate group connected by a flexible tetra(oxyethylene) spacer. The molecule exhibits an unprecedented sequence of layered smectic phases, in the order: smectic A-smectic B-reentrant smectic A. Electron density profiles and large-scale molecular dynamics simulations indicate that competition between the stacking of bicyclohexyl mesogens and the conformational flexibility of tetra(oxyethylene) chains induces this unusual reentrant behavior. Ion-conductive reentrant liquid-crystalline materials have been developed, which undergo the multistep conductivity changes in response to temperature. The reentrant liquid crystals have potential as new mesogenic materials exhibiting switching functions.     

Synthesis,structure and properties of new chiral liquid crystalline monomers and homopolysiloxanes containing menthyl groups

The synthesis is described of four new chiral liquid crystalline monomers (M₂–M₅ ) and their corresponding side‐chain homopolysiloxanes (P₂–P₅ ) containing menthyl groups. Chemical structures were characterised using FT‐IR or ¹H NMR spectra, and specific optical rotations were evaluated with a polarimeter. The phase behaviour and mesomorphic properties of the new compounds were investigated by differential scanning calorimetry, thermogravimetric analysis, polarising optical microscopy, UV/visible/NIR spectrocopy and X‐ray diffraction. The monomers and homopolymers with more aryl segments showed noticeably lower specific optical rotation value. The monomers M₂–M₅ formed a cholesteric or blue phase when a flexible spacer was inserted between the rigid mesogenic core and the terminal menthyl groups by reducing the steric effect. M₂–M₅ revealed enantiotropic cholesteric phase. Moreover, M₂ also exhibited a monotropic smectic A (SmA) phase, and M₄ also exhibited a cubic blue phase on cooling. The selective reflection of light shifted to the long wavelength region with increasing rigidity of the mesogenic core for M₂–M₅ . P₂–P₅ exhibited SmA phases, and the mesogenic moieties were ordered in smectic orientation with their centres of gravity in planes. Melting or glass transition temperature and the clearing temperature increased, and the mesophase temperature range widened with increasing rigidity of the mesogenic core.     

Synthesis and mesomorphic properties of some biphenyl-phenyl triesters as potential longitudinal ferroelectrics

Abstract

A homologous series of “fraternal twin” molecules consisting of relatively short and relatively long mesogenic units connected by a flexible spacer group and flexible chains as the terminal groups was synthesized in an attempt to form a non-chiral longitudinal ferroelectric smectic phase. The shorter of the two mesogenic units consisted of a 4-alkyl/alkoxy substituted biphenyl ester; the longer a terbenzoate group. Mesomorphic properties were determined by hot-stage polarizing microscopy and DSC. Several smectic phases were observed as well as nematic phases. Characterization of the smectic phases by microscopic textures is discussed.     

Trimeric and tetrameric liquid crystalline thiadiazole derivatives

Novel liquid crystalline 2-phenyl-1,3,4-thiadiazole based oligomers with three and four rigid aromatic units linked by a flexible central unit have been investigated by polarizing microscopy. The synthesis of these compounds and the influence of structural variations on the mesomorphic properties are described. The combination of suitable mesogenic moieties with appropriate central units leads to oligomers which exhibit S_c phases.     

Synthesis and study of azo dye compounds: variation of mesogenic behaviour with length of alkyl chains

The mesogenic behaviours of two azo dye liquid crystals, 1 and 4, differ because of the different length of terminal alkyl chains; azo dye 1 shows a SmB phase, azo dye 4 shows nematic and SmA phases during thermal processing. The molecular stackings of these two azo dye liquid crystals are compared on the basis of crystallographic studies to explain such unexpected mesogenic behaviour.     

Some Novel Smectic* Liquid-Crystalline Side-Chain Polymers

Abstract

Three acrylate side-chain polymers in which the mesogenic moieties are based on the 4-n-alkoxyphenyl-4′-(4″-methylhexyloxy) benzoates have been characterized by differential scanning calorimetry, optical microscopy and X-ray diffraction. For shorter flexible spacers (n = 2) both smectic A and C^* phases are observed thus making this polymer interesting for the fabrication of electro-optical devices based on ferroelectric properties (a smectic A phase is required for alignment purposes). For longer flexible spacers, (n = 6, 11) only the smectic A phase remains.     

V-shaped Schiff’s base liquid crystals based on resorcinol: synthesis and characterisation

ABSTRACT

This paper designed and synthesised a series of V-shaped liquid crystal molecules (X-SBA_nE) with resorcinol as the core and Schiff base as the mesogenic arms (X-SBAA_n). The effects of polarity of terminal groups (X=-CH₃O,-CH₃,-Cl) and length of flexible chain (n = 4,6,8) on mesogenic ranges were discussed. The chemical structure of X-SBAA_n and X-SBA_nE was studied using FT-IR and ¹H-NMR while their thermal behaviour and mesogenic ranges were investigated via differential scanning calorimetry (DSC) and polarising optical microscopy (POM). The results indicated that X-SBAA_n containing OCH₃ and Cl substituents exhibited mesophase except for the analogue having CH₃ substituent which was found to be non-mesogenic. All of the synthesised X-SBA_nE had liquid crystal properties and exhibited nematic phases in heating and cooling. The length of the flexible spacers and terminal groups significantly influenced their mesogenic ranges.     

Obituary: Professor Frank M. Leslie FRS (1935-2000)

The synthesis of five new cholesteryl-based monomers (M-1?M-5) and the corresponding smectic comb-like polymers containing cholesteryl groups (P-1?P-5) is presented. The chemical structures were characterised by FT-IR, 1H NMR and elemental analyses. The specific optical rotations were evaluated with a polarimeter. The phase behaviour was investigated by polarising optical microscopy, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction. The specific optical rotation values of these monomers and polymers with the same number of phenyl rings and terminal groups were nearly equal; however, they decreased with increasing the aryl numbers in the mesogenic core. The monomers M-1?M-5 showed oily streak and focal conic optical textures, or finger print textures characteristic of the chiral nematic phase. The polymers P-1?P-5 showed the smectic A phase. The melting, clearing, and glass transition temperatures increased, and the mesophase temperature ranges widened with increasing the aryl number in the mesogenic core. However, although the molecular structures of M-4 and M-5 were similar to those of M-3, namely their mesogenic cores contained three phenyl rings, their phase behaviour differed considerably, and T _m and T _i of M-4 and M-5 were less than those of M-3. In addition, M-4 and M-5 showed a clear glass transition similar to the polymer. Furthermore, the ester linkage bond and aryl arrangement in the mesogenic core also affected the phase behaviour.     

Sensitivity of the NTB phase formation to the molecular structure of imino-linked dimers

ABSTRACT

Here we report on the synthesis and mesomorphic properties of a series of imino-linked dimeric molecules. In order to improve our understanding of the structure–N_TB phase correlations, we have studied the impact of geometric and electronic factors arising from varying mesogenic units, different spacer lengths and from the ratio (n/m) between the lengths of terminal chains (n) and spacer (m). From the perspective of the molecular geometry, the results show that the stability of the N_TB phase results from increasing effective molecular bending and with the broadening of the mesogenic unit, in particular near the spacer, and that the n/m ratio plays a substantial role in conjunction with the specific mesogenic unit. A computational study of the electronic properties shows that a broadening of the mesogenic core in the vicinity of the spacer is associated with an increased anisotropy of the electrostatic potential distribution. Within a given series of materials our study suggests that the incidence of the N_TB phase and its thermal stability are governed by the synergy of specific geometrical factors and the anisotropy of the electrostatic potential distribution of the mesogenic core.     

Functional Janus dendrimers containing carbazole with liquid crystalline,optical and electrochemical properties

ABSTRACT

Novel liquid crystalline Janus dendrimers that combine a mesogenic block and an electroactive block have been synthesised. The mesogenic block is based on two third-generation Percec-type dendrons bearing six or eight terminal dodecyloxy alkyl chains, whereas the electroactive blocks are formed by one or two carbazole units. The liquid crystal behaviour was investigated by polarised-light optical microscopy, differential scanning microscopy and X-ray diffraction. The Janus dendrimers with one electroactive unit exhibited cubic or columnar liquid crystal phases, whereas the Janus dendrimers with two electroactive units did not show liquid crystalline behaviour. The UV-vis absorption and emission properties of the Janus dendrimers were investigated. The spectra suggested the existence of π-π stacking and the formation of aggregates in the solid state. Electrodeposition of the carbazole-containing dendrimers afforded semi-globular particles in which the number of electropolymerizable units and the flexible or rigid character of the linker have a decisive influence in the particle size.     

New chiral liquid crystal monomers and cholesteric polyacrylates: synthesis and characterisation

The synthesis of new chiral monomers (M₁ ?M₃ ) based on menthol and the corresponding polyacrylates (P₁ ?P₃ ) is described. The chemical structures, formula and phase behaviour of the obtained monomers and polymers were characterised with FT-IR, ¹H-NMR, elemental analyses, differential scanning calorimetry (DSC), polarising optical microscopy (POM) and X-ray diffraction (XRD). The effect of the mesogenic core rigidity, spacer length and menthyl steric effect on the phase behaviour of M₁ ?M₃ and P₁ ?P₃ is discussed. The expected mesophase of the compounds based on menthol can be obtained by inserting a flexible spacer between the mesogenic core and the terminal groups. For the chiral monomers and polyacrylates, their corresponding melting temperature (T _m), glass transition temperature (T _g) and clearing temperature (T _i) increased with an increase of the mesogenic core rigidity; while the T _m, T _g and T _i decreased with increasing the spacer length. M₁ and P₁ showed no mesophase, while M₂ and M₃ all revealed a SmC* and cholesteric phases. P₂ and P₃ only showed a cholesteric phase.     

Synthesis and evaluation of a series of novel 2-substituted poly(allylalcohol) side chain liquid crystalline oligomers exhibiting ferroelectricity

Abstract

The recently published Baylis-Hillman methodology has been used to prepare a number of side chain liquid crystalline poly(allylalcohols) incorporating a ferroelectric mesogenic side chain. These poly(allylalcohols) exhibited wide range S?_C phases and, in the case of two of these materials, low glass transition temperatures. The transition temperatures and phase behaviour of the SCLC poly(allylalcohols) were compared to acrylate and methacrylate SCLC oligomers containing a similar mesogenic side chain. The response times for two poly(allylalcohols) exhibiting low glass transition temperatures were also measured over a wide temperature range. Although the poly(allylalcohols) had comparable response times to the analogous acrylate and methacrylate SCLCP, they showed the greater temperature dependence of the response time. However, at 39°C one of the SCLC poly(allylalcohols) showed a response time of 65 ms.     

Fluorinated chiral nematic liquid crystal dimers based on (S)-1-phenylethane-1,2-diol

ABSTRACT

A series of symmetric liquid crystal (LC) dimers with the same chiral core (S)-1-phenylethane-1,2-diol ((S)-PE) have been synthesised, termed TBDA-(S)-PE, 3F3B-(S)-PE, 3F2B-(S)-PE, 1F3B-(S)-PE, 1F2B-(S)-PE, respectively. Chemical structures and LC properties of the five symmetric LC dimers were characterised by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance hydrogen spectrometer (¹H NMR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and polarised optical microscopy (POM). TBDA-(S)-PE displayed enantiotropic chiral smectic A (S_mA*) phase while 3F3B-(S)-PE, 3F2B-(S)-PE, 1F2B-(S)-PE all displayed enantiotropic chiral nematic (N*) phase and 1F3B-(S)-PE displayed monotropic N* phase. The results indicated that the removal of the flexible spacers between the rigid mesogenic arm and the chiral core facilitated the formation of the N* phase. When the rigid mesogenic units are connected to the chiral core directly, the structure of the terminal fluorine group and the rigidity of the mesogenic unit played certain influence on the thermal properties of the LC dimers, but did not change the type of mesomorphic phase. Compared to 3F3B-(S)-PE and 1F3B-(S)-PE, 3F2B-(S)-PE and 1F2B-(S)-PE displayed wider LC ranges, respectively, suggesting molecular regularity had greater influence on LC-isotropic (I) transition temperature.     

Liquid-crystalline fork-like dendrons

ABSTRACT

Dendritic molecules having several rigid-rod moieties can be applied to induce liquid crystallinity for a variety of non-mesomorphic functional molecules such as metal complexes, nanoparticles, fullerenes and π-conjugated molecules when these dendritic molecules are covalently bonded to those non-mesomorphic molecules. These complex molecules are called supermolecular liquid crystals. Due to the cooperation of several mesogenic moieties, these dendritic molecules exhibit very stable liquid-crystalline (LC) phases. We have used fork-shaped LC dendrons having two or three rigid-rod moieties to induce liquid crystallinity for functional molecules such as interlocked molecules and π-conjugated molecules. In these fork-like molecules, the rigid-rod cores are attached to the 3,4,5-position of the phenyl moieties through flexible spacer, and these molecules are bonded to functional molecules through the 1-position. They basically form smectic LC phases, which induce the layered arrangement of functional moieties. Here we report on a new family of fork-like mesogens containing a hydrogen bonding moiety or an ionic group. They are designed to build supramolecular materials.     

Liquid crystal oligomers: going beyond dimers

This review focuses on structure-property relationships in liquid crystal oligomers, which consist of molecules containing two or more mesogenic units linked via flexible spacers essentially in a linear fashion and so does not consider, for example, liquid crystal dendrimers and tetrapodes. Previous reviews have tended to focus mainly on liquid crystal dimers in which just two mesogenic units are interconnected by a single spacer. By contrast, this review is largely devoted to higher oligomers such as liquid crystal trimers and tetramers containing three or four mesogenic units connected by two or three spacers, respectively.     

The chromonic phases of dyes

Abstract

It has been shown that the lyotropic liquid-crystalline phases formed by certain dyes are structurally analogous to the chromonic N and M liquid-crystalline phases previously thought to be unique to certain anti-asthmatic/anti-allergic drugs. We suspect that these two groups of compounds will prove to be representatives of a large new class of mesogenic materials.     

Liquid crystal side chain polysiloxanes containing various proportions of non-mesogenic units

Abstract

Recent studies have established that side chain polymeric liquid crystals composed of mesogenic and non-mesogenic side groups keep their liquid-crystalline properties even for a low proportion of mesogens. We show that the detailed structures of three kinds of new diluted liquid crystal polysiloxanes depend on the nature of the co-substituent as well as on the proportion of the silicon sites occupied by the mesogenic groups. Mixtures of these systems with low molar mass liquid crystals were also investigated in terms of compatibility and/or stabilization of smectic A phases.     

Synthesis and mesomorphic properties of a series of dimers derived from thioether-terminated and cholesteryl

ABSTRACT

The synthesis and material properties of a series of new liquid crystalline compounds containing thioether and cholesteryl, these homologues with different alkyl chain lengths of 2–8, are reported. Thermal analysis shows that all oligomers have wide mesophase temperature ranges with high thermal stability. The oligomers were determined by differential scanning calorimetry (DSC) and polarising optical microscopy (POM). The molecule not only successfully exhibits strong optical properties and rainbow colours, but also the cholesteric helical pitch decreased with increasing temperature. The mesogenic incidence and tendency were found to be strongly dependent on the numbers of carbon in the flexible alkyl chain. Even members formed widely mesophase compared to odd members that showed narrower ones. The reflection wavelengths of 6S8Ch are almost across the entire visible region when they are heated, which offer tremendous potential for various optical applications. Also, it not only shows a lower transition temperature but also has a narrower cholesteric phase compared to analogues with alkoxy groups. These results not only provide practical design principles for the synthesis of new sulphur-containing LC materials with optical applications, also make a significant contribution to use as thermally sensitive liquid crystal devices requiring fast response.