Liquid crystalline dimeric compounds with an alkylene spacer

Two series of compounds with dimeric molecules have been synthesized and characterized. These molecules consist of two non-mesogenic units linked by an alkylene spacer through an ester linkage. The effects of varying the terminal as well as the spacer chain length on the mesomorphic properties have been studied. For compounds with an even number of carbon atoms in the spacer chains, the observed textures in the mesophases are reminiscent of those seen for the smectic phases of banana-shaped molecules.     

Liquid crystalline properties and dependence of transition temperatures on the length of the flexible alkylene spacer of symmetric dimers composed of bent-core units

Three new series of symmetric dimers composed of bent-core molecules connected by a flexible alkylene spacer have been synthesized and their mesomorphic properties studied. The effect of varying the length of the terminal chains for fixed odd and even spacers, as well as varying the spacer length for a fixed terminal chain length, on the mesomorphic properties has been investigated. Remarkably, all the dimers investigated show the same type of mesophase, which has been characterized as a Col_obP_F phase, on the basis of X-ray diffraction and electro-optical measurements. It is found that for a fixed spacer length, the thermal range of the mesophase increases with increase in the number of methylene units in the terminal chain. On the other hand, interestingly an odd-even effect is observed when the length of the flexible spacer is varied; dimers having an odd number of methylene units possess higher clearing points.     

Liquid crystalline phases of perfluorinated compounds with segregated sublayers

The liquid crystalline polymorphism (S_A, S_B, CrE) and the structures of the phases of N-n-perfluoralkylethyl-(4-phenylbenzylidene)imines are described. It is shown that the smectic layer consists of two sublayers in to which the incompatible moieties of the compounds segregate. It is proved that the perfluoralkyl chains remain disordered until crystallization occurs, whereas with decreasing temperature, the aromatic parts are ordered in types of S_B and CrE structure.     

Liquid crystalline thermosets from dimeric LC epoxy resins cured with primary and tertiary amines

Liquid crystalline thermosets (LCTs) were prepared by curing difunctional LC dimeric epoxy monomers with imine moieties in the mesogenic core and central spacers of different length. Primary diamines or tertiary amines were used as curing agents obtaining materials with different characteristics. The results obtained were related to the mesogen structure, since dipolar moments in the mesogenic cores affect the ability to form ordered networks.     

Comparison of liquid crystalline properties of dimeric compounds of different skeletal shapes

Series of dimeric compounds of different skeletal shapes consisting of two triad aromatic ester type mesogenic moieties connected via polymethylene spacers were synthesized and their liquid crystalline properties compared. The two mesogenic units are connected in either Hor T-shape or in linear fashion. In general, it was found that mesophase temperature ranges for the T- and linear-shaped compounds are much wider than for the H-shaped compounds. Moreover, the former are enantiotropic thermotropic materials, whereas the latter tend to be monotropic unless the spacer length is fairly long, i.e. longer than decamethylene. Among the three series, the linearly linked twin compounds had the highest melting and isotropization temperatures. All of the linear and T-shaped dimeric compounds reported in this article form only nematic mesophases.     

Comparison of liquid crystalline properties of dimeric compounds of different skeletal shapes

Series of dimeric compounds of different skeletal shapes consisting of two triad aromatic ester type mesogenic moieties connected via polymethylene spacers were synthesized and their liquid crystalline properties compared. The two mesogenic units are connected in either Hor T-shape or in linear fashion. In general, it was found that mesophase temperature ranges for the T- and linear-shaped compounds are much wider than for the H-shaped compounds. Moreover, the former are enantiotropic thermotropic materials, whereas the latter tend to be monotropic unless the spacer length is fairly long, i.e. longer than decamethylene. Among the three series, the linearly linked twin compounds had the highest melting and isotropization temperatures. All of the linear and T-shaped dimeric compounds reported in this article form only nematic mesophases.     

Liquid crystalline compounds with V-shaped molecular structures: synthesis and characterization of new azo compounds

The synthesis and mesomorphic properties of a series of 1,2-phenylene bis[4-(4-alkyloxyphenylazo)benzoates] are reported. The mesophases exhibited by these bent-shaped azo compounds are identified as nematic, smectic A and crystal E phases. All these compounds have fairly low transition temperatures, and so are suitable for physical studies. It has been concluded that the -CH N- linkage can be more conducive to mesomorphism compared with the -N N- linkage.     

Liquid crystalline copolymers containing electron donor and acceptor mesogens with a chiral group in the spacer unit

Side-chain liquid crystalline polymers containing both mesogenic (carbazolylmethylene)aniline and (4′-nitrobenzylidene)aniline units with various spacer groups were prepared to examine effects of the structure of spacer groups on the liquid crystalline properties. The copolymer containing (R)-(+)-2-methylpropylene as a chiral group in the spacer unit induced a smectic phase; the copolymer with a trimethylene spacer of similar length to the chiral spacer exhibited a nematic phase. Smectic phases were observed for the copolymer containing the chiral spacer group when the proportion of the carbazolyl group was in the range of 0.55–0.88. For example, the copolymer with the proportion of the carbazolyl group of 0.68 expressed the smectic phase from 88° to 167°C. This isotropic temperature was 37° higher than the calculated value (130°C) based on an assumed copolymer composition without the electron donor–acceptor interaction. Thus, it is assumed that for the chiral copolymer containing both electron donor and acceptor groups, the thermal stability and the induction of the smectic phase were caused by both the electron donor–acceptor interaction and the existence of the chiral group in the spacer unit. © 1995 John Wiley & Sons, Inc.     

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.     

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.     

Liquid crystalline complexes of an azo-containing surfactomesogen with oppositely charged polyelectrolytes

A triethyl-ammonium functionalized 4-nitro-4′-alkoxy azobenzene mesogen with a 10-carbon spacer (azo10Q, a ‘surfactomesogen’) was complexed in equimolar proportions to a variety of oppositely charged polyelectrolytes, and studied by differential scanning calorimetry (DSC), polarizing optical microscopy, and X-ray diffraction. The complexation generates a single-layer smectic A mesophase over a very wide temperature range from a surfactomesogen that, alone, melts directly to the isotropic phase. The clearing temperatures, ranging from 130 to 190 °C and generally higher than the melting point of azo10Q, are dependent on the nature of the polyelectrolyte as well as its molecular weight. In contrast, a prominent glass transition near ambient temperature appears to be independent of molecular weight, but varies somewhat with the type of polyelectrolyte. A second T_g-like transition of much lower intensity is detectable at higher temperatures (generally above 100 °C), and, with literature support, is tentatively attributed to nanophase separation involving sublayer planes in the lamellar packing structure. A series of nonequimolar complexes was also investigated, and it was found that, with decreasing azo10Q content, the clearing temperature viewed by DSC decreases rapidly in intensity (and somewhat in temperature) and then disappears although birefringence remains, whereas the lower glass transition increases rapidly in temperature to finally merge with the upper one. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3421–3431, 2005     

Liquid crystalline properties of new unsymmetrical compounds with benzothiazole core detected by TG/DSC-POM-XRD

Thermal properties of two azomethine liquid crystals with a benzothiazole core were synthesized and investigated by applied Mettler-Toledo AG equipment (TG/DSC). Azomethines with benzothiazole core was obtained by nucleophilic addition of benzothiazole-2-carboxaldehyde in N,N-dimethylacetamide (DMA) solution with 4-(heptadecafluoroctyl)aniline (BTA1) or 4-hexadecylaniline (BTA2). The differential scanning calorimetry (DSC) was employed to evaluate their phase transitional behavior. Variable heating and cooling rates were used to study liquid crystalline properties of azomethines with benzothiazole core. Compound BTA1 exhibited liquid crystalline properties, while BTA2 is non-mesogenic. Three or four endothermic DSC peaks were observed for both compounds during heating process with the rate 0.5?°C/min. The mesophase was identified and confirmed by XRD study and polarized optical microscopy (POM) too. The thermal stability was determined by thermogravimetric analysis (TG). The temperatures of 5% mass loss (T _5%) of BTA1 and BTA2 range from 212 to 317?°C in nitrogen.     

Novel liquid crystalline compounds having an enyne unit

Novel series of liquid crystalline compounds having an enyne unit, 1-(4-alkylphenyl)-4-(trans-4-alkylcyclohexyl)-but-3-en-1-yne and 1-(4-alkoxyphenyl)-4-(trans-4-alkylcyclohexyl)-but-3-en-1-yne are presented. The synthetic methods, mesomorphic phases, and some physical properties of these series are reported.     

Liquid crystalline calixarenes

Bowl-shaped (bowlic) liquid crystals are reviewed and new bowlic materials containing rigid tungsten-oxo calix[4]arene based cores are discussed. Tungsten-oxo calix[4]arenes with 8 and 12 dodecyloxy sidechains have been investigated and exhibit bowlic columnar phases which are stable over approximately a 200° temperature range. The uncomplexed tetra-phenol ligands display only a transient liquid crystallinity on the first heating, and the conformational rigidity provided through tungsten-oxo complexation is necessary for well behaved mesomorphism. For the 8 sidechain analog the clearing point is at 320°C and the addition of four more sidechains results in a lower clearing point at 267°C. Polarized optical microscopy and DSC indicate that the 12 sidechain analog displays a phase with the columns packed in a hexagonal lattice which is conductive to the formation of polar phases. Both complexes exhibit a pronounced tendency to bind Lewis base guests in their cavities, and DMF forms very strong complexes which were spectroscopically characterized. The DMF guest produces large effects on the phase behavior by suppressing mesomorphism and lowering the isotropic points by 115°C and 84°C for the 8 and 12 sidechain compounds respectively. This extreme sensitivity to the DMF guest is conclusive proof that bowlic tungsten-oxo calix[4]arene liquid crystals organize in head-to-tail structures.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Liquid crystalline photoconductors

Abstract

The influence of molecular order as well as of orientation of charge carrier units on photoconductivity has been investigated for the liquid crystal photoconductors H5T (1), thiadiazole (2) and oxadiazole (3). The discotic H5T (1) and both smectic systems 2 and 3 exhibit a higher photocurrent in the highly ordered mesophase than in the polycrystalline or isotropic state. For 1, results concerning charge carrier transport mechanism and Dember effect are given indicating an electronic charge transport comparable with the one known for single crystalline anthracene.     

Liquid crystalline networks

The last 2 years have seen significant advances in synthesis, physical experiment and theory. Highlights include the experimental confirmation of the soft elasticity effect and the penetration of the ideas of random disorder into the field of polymer structure and rheology.     

Liquid crystalline photoconductors

The influence of molecular order as well as of orientation of charge carrier units on photoconductivity has been investigated for the liquid crystal photoconductors H5T (1), thiadiazole (2) and oxadiazole (3). The discotic H5T (1) and both smectic systems 2 and 3 exhibit a higher photocurrent in the highly ordered mesophase than in the polycrystalline or isotropic state. For 1, results concerning charge carrier transport mechanism and Dember effect are given indicating an electronic charge transport comparable with the one known for single crystalline anthracene.     

Liquid crystalline polymers

The suitabilities of thermo-optometry and differential scanning calorimetry for the characterization of certain copolyethers were compared. Under certain conditions, such polymers do not exhibit the endotherm signal corresponding to the solid/liquid crystalline transition in the DSC curves. Thermo-optometry provides evidence of these phase transitions into the liquid crystalline state, and is a very useful additional method.