Experimental studies on the B7 phase of a banana-shaped achiral mesogen

We report optical, X-ray, polarization and response time measurements on a new 'bananas-haped' mesogen. The material has a salicylaldimine segment in the linear part of the core, but is otherwise structurally similar to the mesogen first reported to show a banana mesophase. Textural and X-ray studies show that this mesophase has all the characteristics of the recently discovered B₇ phase. It is observed that the voltage required to obtain electrical switching is quite low compared with values for the few other materials exhibiting the B₇ phase.     

Occurrence of the B 7 mesophase in two homologous series of seven-ring achiral compounds composed of banana-shaped molecules

The synthesis and mesomorphic behaviour of twenty compounds belonging to two new series of seven-ring esters derived from 2-cyanoresorcinol are reported. Many homologues of both series exhibit the B₇ mesophase. In addition, some of the lower homologues exhibit a mesophase which shows textural features similar to that of the two-dimensional B₁ phase. The characterization of the mesophases has been carried out using polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction, miscibility studies and electro-optical investigations. The first example of a plot of the B₇-isotropic phase transition temperature as a function of the alkyl chain length is also reported.     

Ferroelectric switching in a novel bent-shaped mesogen having two non-mesogenic units linked by an alkylene spacer

We report the synthesis, X-ray diffraction results and electro-optical switching measurements for a bent-shaped mesogen having two non-mesogenic units linked by an alkylene spacer. The novelty of the molecular structure lies in the carbonyl group of the ester linkage being directly attached to the spacer unit, unlike for banana-shaped molecules reported so far, in which it is one oxygen atom away from the spacer or the central aromatic unit. The compound shows two mesophases: the high temperature mesophase is a tilted smectic phase showing ferroelectric switching characteristics; the low temperature phase is more highly ordered with textural features similar to that of the B₃ banana phase.     

The binary system composed of a bent-core compound forming a B7 phase and a nematogenic calamitic compound

The isobaric phase diagram for a binary system of liquid crystals is presented. One mixing component is a bent-core mesogen forming a B₇ phase and the other one is a nematogenic calamitic compound. The occurring mesophases have been identified by their optical textures as well as by X-ray investigations. The B₇ phase exists down to about 60 mol% of the bent-core compound A / 40 mol% of the calamitic compound B. Two additional mesophases are induced in the mixed phase region. At medium concentrations (around 50 mol%) an oblique columnar phase appears which shows a similar X-ray pattern to the B₇ phase but an utterly different nucleation on cooling the isotropic liquid and a completely dissimilar texture. At concentrations below 35 mol% A, a further phase is induced which possesses an irregularly modulated layer structure. This phase can be regarded as an intermediate state between the regularly modulated Col_r (B₁) phase and the intercalated B₆ phase. It transforms on cooling into the phase with a regularly modulated structure.     

SmA-SmC-B2 polymorphism in an achiral cyano substituted banana-shaped mesogen

A new achiral five-ring banana-shaped mesogen is presented which has a cyano substituent in the 4-position of the central core. Microscopical, X-ray, dielectric and electro-optical investigations give evidence for the unusual phase sequence B₂, SmC, SmA. The B₂ phase shows an antiferroelectric switching behaviour; the spontaneous polarization was found to be 330 nCcm^-2.     

Azo functionalised achiral bent-core liquid crystals: observation of photo-induced effects in B7 and B2 mesophases

Three structural variants of azo substituted achiral bent-core compounds are reported. Here, the effect of symmetrical and non-symmetrical arms at 1,3-positions of the central phenyl ring on the mesogenic properties of the resulting bent-core azo compounds is studied. The structures of all the compounds synthesised are confirmed by the organic spectroscopic methods. The liquid crystalline properties are investigated using polarising optical microscopy, differential scanning calorimetry and X-ray diffraction studies. It was found that the non-symmetrical molecules are more conducive to mesomorphism than the symmetrical ones. We observed B₁ (Col_r), B₂ (SmC_AP_A) and B₇ mesophases in these compounds. The B₇ mesophase was found to have a modulated layer structure. Interestingly, a reversible field-induced transition from the B₇-like structure to the racemic SmC_AP_F was also observed. We also report the photo-induced studies in the B₇ mesophase and make a comparison of these results with those obtained in a B₂ mesophase. From our studies, we observed that these effects are more profound in the case of B₇ mesophase when compared to the B₂ mesophase in such systems.     

Novel mesophases in fluorine substituted banana-shaped mesogens

A new homologous series of achiral banana-shaped mesogens ('Dn') has been synthesized and studied by the classical techniques (optical microscopy, differential scanning calorimetry, X-ray diffraction, miscibility studies and electro-optic investigations). The short homologues (D6-D8) exhibit a two-dimensional phase 'B1_x' different from a B1 phase with a rectangular lattice. The longer homologues (D9-D14) present a mesophase which displays the defects of the B7 phase of the PIMB-NO₂ compounds. Nevertheless the D9-D14 mesophase is not miscible with the B7 phase, and contrary to B7, exhibits a bistable behaviour ('ferroelectric' type) suggesting at least a B7 variant.     

Bent-core mesogens with biphenyl moieties: observation of a B7 to B4 phase transition

Four new bent-core mesogens containing biphenyl moieties are reported. All these, except the first homologue, exhibit B₇ and B₄ banana phases, both of which are known to have a helical structure. The B₇ to B₄ phase transition is very rare, this being perhaps only the second report of the observation of such a phase sequence. The first homologue exhibits only one mesophase X₁ with textural features reminiscent of the B₁ phase. All the compounds synthesized are characterized by spectral data. The mesophases exhibited by these compounds are characterized by polarizing optical microscopy, differential scanning calorimetry and X-ray studies.     

枝杈状Bola型两亲分子包覆的层状近晶相多金属氧簇液晶

我们利用离子自组装的方法以含苯甲酸基团的两亲分子A6包覆了含铕的无机多金属氧簇Na9[EuW10O36]。利用红外光谱、热重分析、元素分析等方法对所得有机无机杂化复合物A6Eu进行了详细的结构表征。苯甲酸基团通过分子间氢键相互作用发生的二聚使有机组分形成了枝杈状的Bola型结构,这种结构导致外围的介晶基元以侧向方式连接在无机簇上。我们通过差示扫描量热法、偏光显微镜和变温X射线衍射对A6Eu的热致液晶性质进行了表征。虽然单独的两亲分子A6组装成了简单的近晶结构,但是复合物A6Eu表现出新颖的层状近晶相液晶结构。层状近晶相液晶结构中介晶基元是平行于层面的。由此可见,介晶基元的侧向连接方式对复合物的热致组装结构具有重要影响。多金属氧簇的荧光性质在液晶材料中得到了很好的保持。     

Synthesis and mesomorphic properties of calix[4]resorcinarene–triphenylene oligomers

By controlling the mol ratios of reactants, novel calix[4]resorcinarene–triphenylene monomer, dimer and tetramer were designed and synthesised in yields of 50–60% via Click chemistry. Their structures were characterised by NMR and MS. Their liquid crystalline behaviours were studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction analysis. The more triphenylene units on calix[4]resorcinarene resulted in the wider temperature scopes of mesophase and higher phase transition temperatures. The monomer 6 and dimer 7 showed the mixed columnar mesophase with hexagonal columnar structure and disordered lamellar columnar structure, and compound 8 possessed only disordered lamellar columnar mesophase. These research results suggest that calix[4]resorcinarene was a good platform to construct columnar liquid crystal and the mesomorphic properties were greatly influenced by the substituted numbers of mesogen units on calix skeleton.     

Chiral ordering in the nematic and an optically isotropic mesophase of bent-core mesogens with a halogen substituent at the central core

Two new homologous series of bent-core compounds have been synthesized. Their mesophase behaviour has been investigated by polarizing microscopy, differential scanning calorimetry, X-ray diffraction, NMR spectroscopy, and by dielectric and electro-optical measurements. It was found that, with one exception, all the chlorine-substituted compounds form a nematic phase and an optically isotropic ‘banana phase’. The latter phase shows spontaneously chiral domains of opposite handedness. This phase may be considered as a type of smectic blue phase. The mesophase behaviour of the homologous bromine-substituted compounds is more complicated. Depending on the chain length, B₆, columnar, nematic or the isotropic ‘banana phase’ occur.     

Synthesis and characterization of N‐substituted polyaniline with mesogen molecules

The N‐substituted polyaniline (PANi) was synthesized by incorporation of bromine‐terminated mesogens onto the emeraldine form of polyaniline. Firsty three liquid crystalline molecules containing biphenyl units were synthesized. These mesogenic molecules are named as: 6‐bromo‐ (4‐hexyloxy‐biphenyl‐4′‐oxy) hexane (C₆? C₆Br), 5‐bromo‐(4‐hexyloxy‐biphenyl‐4′‐oxy) pentane (C₆? C₅Br), 6‐bromo‐(4‐octyloxy‐biphenyl‐4′‐oxy) hexane (C₈? C₆Br). Differential scanning calorimetry (DSC) in combination with polarizing optical microscopy (POM) were used to investigate the thermal properties of them. Optical microscopy showed focal conic texture characteristic of the Smectic A phase for (C₆? C₅Br) and (C₈? C₆Br). For (C₆? C₆? Br) smectic phase was determined. DSC experiments were also found in accord with mesophase formation. For the synthesis of N‐substituted polyaniline with these mesogen molecules, the emeraldine base polyaniline was reacted with BuLi to produce the N‐anionic polyaniline and then deprotonated polyaniline was reacted with bromine‐end mesogen to prepare mesogen‐substituted polyaniline through N‐substitution reaction. The degree of N‐substitution can be controlled by adjusting the molar feed ratio of mesogen to the number of repeat units of PANi. The microstructure and compositions of obtained polymers were characterized by FT‐IR, elemental analysis, DSC, and scanning electron microscopy (SEM). The cyclicvoltammetry show that the electroactivity of N‐substituted polyaniline is strongly dependent on the degree of N‐grafting. The solubility of mesogen‐substituted polyaniline in common organic solvents such as THF and chloroform was improved by increasing the degree of N‐substitution and also the samples are partially soluble in xylene. Liquid crystalline behavior of mesogen‐substituted polyanilines was investigated via POM, but no mesophase was observed. Copyright © 2008 John Wiley & Sons, Ltd.     

Banana-shaped mesogens: a new homologous series of compounds exhibiting the B7 mesophase

The synthesis and characterization of a new homologous series of compounds, the 2-cyano-1,3-phenylene bis[4-(4-n-alkoxyphenyliminomethyl)benzoates] derived from 2-cyanoresorcinol is reported. All the compounds are enantiotropic mesogens and exhibit the fascinating B₇ mesophase. The characterization of the mesophase was performed using polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical studies.     

Influence of halogen substituent on the mesomorphic properties of five-ring banana-shaped molecules with azobenzene wings

Three new series of bent-shaped molecules with 4-chlororesorcinol, 4-bromoresorcinol or 4-fluororesorcinol as the central unit, and azobenzene with different alkoxy chain length as side arms were synthesised. The mesophase behaviour was investigated by polarising optical microscopy, and differential scanning calorimetry. A representative example has also been characterised by X-ray diffraction (XRD) studies. It is found that almost all of the materials prepared are monotropic liquid crystalline. Depending on the substituent at the central unit and on the chain length nematic phases, B₆ phases, a B₄-like dark conglomerate phase and a modulated/undulated anticlinic SmC phase were found. As a unique feature, upon reducing the chain length a transition from nematic to B₆-type smectic phases was observed, which is reverse to usually observed phase sequences. The UV–vis absorption spectroscopy was also performed to study the effect of light-induced trans–cis-isomerisation on the prepared compounds.     

Mesomorphic properties of copolyesters of 3,6-linked triphenylene-based units and polymethylene spacers

Main chain discotic liquid crystalline polymers consisting of triphenylene-based units and alkyl spacers (C8, C10 and C12), connected by ester linkages in the 3- and 6-positions of triphenylene, have been synthesized and their mesomorphic properties were studied by DSC, polarizing optical microscopy and X-ray diffraction. It was found that these polymers exhibit a hexagonal columnar (Col_h) mesophase with intracolumnar order over a wide temperature range. The clearing temperature decreases on increasing the spacer length. It was found that the clearing temperatures are rather higher than that of the corresponding triphenylene monomer having six hexyloxy chains. These polymers form an ordered columnar mesophase, while the corresponding monomeric mesogen shows a disordered columnar phase. In the polymeric system, the fluctuations of the disc-like units in the mesophase are restricted by the connection of the mesogenic units, which stabilizes the columnar mesophase.     

Antiferroelectric liquid crystal from a banana-shaped achiral molecule

A new banana-shaped achiral compound, 1,3-phenylene bis[4-(3-fluoro-4-n-octyloxyphenyliminomethyl)benzoate] (PBFOB) was synthesized and its antiferroelectric liquid crystallinity determined. The PBFOB was characterized by differential scanning calorimetry, X-ray diffractometry in the small and wide angle regions, and polarizing optical microscopy; its polarization and antiferroelectric properties were also investigated. The presence of a lateral fluoro-substituent in the banana-shaped achiral molecules containing a Schiff's base mesogen induced a decrease in melting temperature and formation of the switchable smectic B₂ phase in the melt. The spontaneous polarization for PBFOB was about 250 nC cm^-2 and the polarization of this phase switched on the reversal of an applied electric field.     

New Architectures for Side Chain Liquid Crystalline Polymers with Chiral Smectic C Mesophases

All attempts at synthesizing side chain liquid crystalline polymers (SCLCPs) with chiral smectic C (s_c*) mesophases simply functionalize one terminal group of the mesogen with a chiral substituent and attach the other terminus to the polymer backbone through a spacer. If a s_c* mesophase is observed, it is usually in the less desirable s_c*-s_A phase sequence. We propose that SCLCPs with laterally attached (vs terminally attached) mesogens offer an ideal architecture for obtaining s_c* meso- phases. This is because extended mesogens symmetrically disubstituted with long n-alkoxy groups can be attached to the polymer backbone through a chiral spacer. Thus, mesogens which typically form the desirable s_c*-n phase sequence can be used, and the chiral group can be introduced at the center of the mesogen which should result in high values of spontaneous polarization. We are not only using mesogens which exhibit s_c*-n phase sequences, but are also attempting to induce smectic layering into laterally attached systems which typically form nematic mesophases by electron-donor-acceptor interactions and immiscible hydrocarbon/fluorocarbon components. Smectic layering was successfully induced in 2,5-bis[(4'-n-alkoxybenzoyl)oxy]toluenes when the n-alkoxy substituents were terminated with perfluorinated segments.     

Effect of Metal Complexation on the Behavior of Liquid Crystalline Polymer

Liquid crystalline side-chain polymers (3b-3f) crosslinked by a trans Pt(II) complex were synthesized by a ligand exchange reaction with dichlorobis(benzonitrile)platinum(II) and poly(methylsiloxane) (3a) bearing a p-cyanobiphenyloxy mesogen unit attached to the polymer backbone by a flexible spacer group. The amount (x) of p-cyanobiphenyloxy mesogen coordinating to the Pt(II) ion in polymers 3b, 3c, 3d, 3e, and 3f was 4.9, 9.7, 14.8, 20.2, and 49.6 mol%, respectively. The effect of Pt(II) coordination on the thermotropic liquid crystalline behavior of 3a was examined by DSC, x-ray diffraction, and polarizing microphotography. Polymers 3a-3d exhibited a nematic mesophase between T_g and T_c. On the other hand, 3e-3f, which have a large amount of Pt(II)-coordinating mesogen, did not show a definite nematic mesophase, but exhibited an ambiguous one. The introduction of Pt(II) ion into 3a resulted in a crosslinked structure and consequently prevented the formation of the ordered nematic mesophase.     

3-Cyano thiophene-based π-conjugated mesogens: XRD and 13C NMR investigations

3-Cyano thiophene-centred π-conjugated mesogens with alkoxy phenyl/biphenyl rings are synthesised by palladium acetate-catalysed direct arylation to investigate the mesophase properties and the molecular order. The synthesised mesogens mostly exhibit smectic A mesophase as confirmed by X-ray diffraction studies. Further, due to the manifestation of π-conjugated core, the mesogens exhibit photo luminescence in solution with emission maxima in the range 425–460 nm. Density functional theory and time-dependent density functional theory calculations of a representative mesogen indicate possible intramolecular charge transfer transition between the biphenyl to 3-cyanothiophene units. Despite structural simplicity, the observation of smectic A phase is attributed to location of strong dipole moment component perpendicular to the long axis of the molecules due to the presence of polar cyano group at 3-position of central thiophene ring. The ¹³C NMR studies are performed in mesophase and using the ¹³C–¹H dipolar couplings determined from 2D separated local field experiment; the order parameters of central thiophene ring and side arm phenyl rings are calculated. Moreover, the order parameter ratios of thiophene and side arm phenyl rings indicate the bent–core nature of the mesogen.     

Effect of lateral substituents on the mesophases formed by some achiral banana-shaped molecules

Several compounds composed of banana-shaped molecules and exhibiting mesophases are reported. The effect of different lateral substituents on the type of mesophase formed is examined and a comparison made with unsubstituted compounds. The mesophases have been characterized using techniques such as polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction. The B₂ phase shows antiferroelectric switching behaviour.