Odd-even effects in the phase transition behaviour of novel U-shaped liquid crystals

A homologous series of U-shaped dimeric liquid crystals in which two mesogenic groups are connected via catechol has been prepared and the effects of terminal alkyl chains, alkyl spacers and core structures on the transition properties investigated by means of optical microscopy and differential scanning calorimetry. The phase sequence exhibits a pronounced odd-even effect as the length and parity of the spacers is varied, in which the even members favour the nematic and smectic C phases, whereas the odd members favour the nematic and smectic A phases. We discuss the transition behaviour of the U-shaped compounds in terms of molecular shape.     

Competition between micro-segregation and anti-parallel alignment of an amphiphilic rod-like liquid crystal

Recently, we reported that a rod-like molecule, 4-[4-(7-hydroxyheptyloxy)phenyl]-1-(4-hexylphenyl)-2,3-difluorobenzene, exhibited a nematic phase with a layered structure and smectic C phases consisting of three states. We prepared a homologous series of the rod-like molecules in which a 2,3-difluoro-1,4-diphenylbenzene unit and a hydroxyl unit are connected via a flexible methylene spacer. We investigated their physical properties using polarised optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). Although they showed nematic, smectic A and smectic C phases, the phase structures were found to depend on the flexible spacer length. Those compounds possessing a shorter spacer length than a heptyl unit exhibited bilayered smectic A and smectic C phases, whereas those possessing a longer spacer length than a heptyl unit showed conventional monolayered smectic A and smectic C phases. A nematic phase with a smectic-like layer ordering was observed for the compound possessing an octyl unit. The structure–property relations of the amphiphilic compounds are discussed.     

具有氟烷基边链和手性中心液晶化合物的合成及液晶性研究

本文设计合成了十个含氟烷基边链和手性中心的液晶化合物，并通过DSC和偏光显微镜对它们的液晶性进行了研究。其中二环系液晶化合物不显示液晶相或仅显示单边近晶A相。三环系液晶化合物中较长的氟烷基边链有利于近晶相的形成，且当液晶核另一端的烷氧基链的长度适中时，在氟烷基边链和液晶核之间具有手性中心的液晶分子显示了手性近晶C相和其它液晶相。     

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.     

Effects of chain branching and lateral fluorine substitution on mesomorphism of cholesteryl benzoates

The mesogenic cholesteryl 4′-alkoxyphenyl-4-carboxylates possessing terminal normal/branched/saturated/unsaturated alkyl chains with laterally ortho/meta substituted electronegative fluorine atom are described. All the homologues exhibited enantiotropic mesomorphism. Smectic A phase, chiral nematic, blue phase (BP) and TGB_A phases were observed in different homologues. All the novel compounds were characterised by spectroscopic and elemental analysis. Thermal investigations and mesophase characterisations for all the compounds were carried out by the combination of DSC, POM and X-ray analysis. The effects of the various terminal normal/branched/saturated/unsaturated alkyl chains and the position of the substituted fluorine atom with its structurally related compounds have been discussed.     

Novel diphenylacetylene-based room-temperature liquid crystalline molecules with alkylthio groups,and investigation of the role for terminal alkyl chains in mesogenic incidence and tendency

In this study, we offer a new family of alkylthio-containing diphenylacetylene-based liquid crystalline molecules (the so-called tolanes) showing nematic phases stable down to room temperature and high birefringence, with insights into the role for terminal alkyl chains in mesogenic incidence and tendency. A number of asymmetric tolane homologues having various alkyl chain lengths in the alkylthio and alkyl groups at each p-, p’-position were synthesised, and their phase transition behaviour was investigated by polarising optical microscope observation, differential scanning calorimetry and wide-angle X-ray diffraction measurement. Consequently, several homologues exhibited monotropic nematic or highly ordered smectic (soft crystal) phases stable down to room temperature. It is found that a long alkyl group on the side opposite to an alkylthio group is prerequisite for mesogenic incidence. In addition, a nematogenic homologue exhibited a higher birefringence value of 0.20 compared to that of 0.19 for an alkoxy counterpart.     

Amphiphilic taper-shaped oligomer exhibiting a monolayer smectic A to columnar phase transition

We prepared two series of liquid-crystalline oligomers composed of phenylpyrimidine based mesogenic cores, alkyl spacers and semiperfluorinated alkyl chains in one series and only alkyl chains in the second series. Their physical properties were investigated using optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. The oligomers possessing a semiperfluorinated alkyl chain show a phase sequence of SmC–SmA–Col when the number of phenylpyrimidine moieties was increased. The compound possessing three phenylpyrimidine cores was found to exhibit monolayer SmA and Col phases. On the other hand, the oligomer composed of an alkyl chain and three phenylpyrimidine cores showed only a nematic phase. We discuss effects of the shape amphiphilicity and the hydrocarbon–fluorocarbon amphiphilicity on phase transition behaviour of the amphiphilic oligomers.     

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.     

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.     

Stripe instabilities in the menisci of free-standing smectic films: influence of the phase sequence of the mesogenic material

We briefly report experimental observations of striped patterns in the menisci of free-standing smectic C films. The results were obtained with a mesogenic compound that transits directly from the nematic phase to the smectic C phase, without an intermediate smectic A phase. In this case, it is shown that stripes do not correspond to undulations of the smectic free surface and smectic layers, as was indeed evidenced in previous studies with other compounds and different phase sequences. Hence, our results show that the nature of striped patterns in free-standing films depends on the phase sequence of the considered materials. Further experimental and theoretical works are still required to fully elucidate the physical mechanisms that drive the onset of patterns in such systems.     

Non-symmetric chiral isoflavone dimers: synthesis,characterisation and mesomorphic behaviour

A new series of non-symmetric chiral isoflavone-based liquid crystalline dimers, α-(2-methylbutyl-4′-(4″-phenyloxy)benzoate)-ω-(3-(4′-decyloxyphenyl)-4H-1-benzopyran-4-one-7-oxy)alkanes, with 3–12 carbon atoms in the alkyloxy spacer, have been synthesised. A pronounced odd–even effect for the phase transition temperatures upon varying the spacer length was observed. The short dimers exhibited monolayer smectic A (SmA) and smectic C (SmC*) phases while for longer homologues a chiral nematic (N*) phase was found. The temperature range of the nematic phase was broadened with elongation of the alkyl spacer. Stabilisation of the nematic phase resulted from competition between the monolayer and intercalated smectic structures. The SmA–SmC* phase transition was second order for all studied compounds with a cross over to the de Vries type behaviour for the shortest homologue.     

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

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.     

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.     

Synthesis and properties of fluorine tail-terminated cyanobiphenyls and terphenyls for chemoresponsive liquid crystals

ABSTRACT

A series of fluorine tail-terminated alkoxy and alkyl cyanobiphenyl compounds and some cyano-p-terphenyl derivatives were synthesised and mesogenic properties described. Comparison with the non-fluorinated K series and M series indicates that the terminal fluorine atom generally decreases the transition temperatures and, more interestingly, depresses the formation of a smectic phase. Several binary LC mixtures formed by the fluorine tail-terminated compounds were found exhibiting promising room temperature nematic phases with wide ranges. The mixture F7OCB and F8OCB shows homeotropic ordering at the metal salts-decorated surfaces and planar ordering at the free surface, which may have potential application in designing a more sensitive and faster LC system to targeted analytes.     

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.     

Creation of nematic and reentrant nematic phases in bi- and multi-component smectic mixtures

Abstract

Experimental results referring to the transformation of smectic phases, mainly smectic A, into nematic and reentrant nematic phases are reviewed. A new explanation of some experimental results is proposed. Factors which are responsible for the depression of smectic phases in mixtures of polar mesogens are discussed and the possibility of forming mixtures with a broad temperature range of nematic phase from smectic compounds, which can be useful for liquid crystal displays (LCDs), is shown. A nematic gap observed in some cases between monolayer (S_A1) or monolayer and partially bilayer (S_Ad) smectics results from the differences in the organization of the molecules in the smectic layers. It is concluded that polar phase from smectic A₁ phases can be divided into two groups: (a) the first one is characteristic for compounds with the -NCS, -F, -CI, -I or ?COC _m H_{2m + 1} terminal group. The spacing of the smectic layer slowly expands with the increase in alkyl chain length and the structure of the smectic A₁ phase slowly changes to be more like the smectic A_d phase (d/1 > 1). It is proposed that such a smectic is called an enhanced monolayer smectic (S_A1e (b) the second one is typical for compounds with the -CN terminal group. This kind of smectic A₁ phase is rapidly transformed into the smectic A_d phase with increasing alkyl chain length. These latter monolayer mesogens easily form the reentrant nematic phase when they are mixed with other polar smectic mesogens.     

Synthesis and mesophase behaviour of mesogens bearing omega, alpha, alpha-trihydroperfluoroalkoxy end tails

One series of two-ring and two series of three-ring liquid crystal compounds, all containing omega, alpha, alpha-trihydroperfluoroalkoxy terminal tails, were prepared and characterized by IR, NMR, MS and elemental analysis. Their phase transition behaviour was investigated by DSC and polarizing optical microscopy. Biphenylene derivatives with the omega, alpha, alpha-trihydroperfluoroalkoxy end group form a stable smectic A phase. In the three-ring system, biphenylene ester compounds exhibit a smectic phase without a nematic phase. The compounds exhibit smectic A and smectic C phases when the terminal groups are intermediate length alkyl and fluorinated alkyl chains. Mesogens with fluorinated tails have a broader smectic C phase than the non-fluorinated mesogens.     

Mesophase formation in a system of top-shaped hard molecules: density functional theory and Monte Carlo simulation

We present the phase diagram of a system of mesogenic top-shaped molecules based on the Parsons-Lee density functional theory and Monte Carlo simulation. The molecules are modeled as a hard spherocylinder with a hard sphere embedded in its center. The stability of five different phases is studied, namely, isotropic, nematic, smectic A, smectic C, and columnar phases. The positionally ordered phases are investigated only for the case of parallel alignment. It is found that the central spherical unit destabilizes the nematic with respect to the isotropic phase, while increasing the length of the cylinder has the opposite effect. Also, the central hard sphere has a strong destabilizing effect on the smectic A phase, due the inefficient packing of the molecules into layers. For large hard sphere units the smectic A phase is completely replaced by a smectic C structure. The columnar phase is first stabilized with increasing diameter of the central unit, but for very large hard sphere units it becomes less stable again. The density functional results are in good agreement with the simulations.     

Synthesis and thermal properties of liquid-crystalline polyacrylates containing a carbazolyl group in the mesogen

The new acrylate monomers 4-(ω-acryloyloxyalkyloxy)-N-(9-methyl-2-carbazolylmethylene) anilines containing from 2 to 11 methylenic units in their alkyl group and a carbazolyl group in the mesogenic unit were synthesized and polymerized by azobisisobutyronitrile (AIBN) as radical initiator and by low-energy electron beam (EB) initiation. The thermal properties of the resulting polymers were examined using differential scanning calorimetry and thermal optical polarizing microscopy. The polymer prepared by AIBN with a hexamethylene spacer exhibited a nematic phase from 73 to 170°C and with an undecamethylene spacer exhibited a smectic phase from 55 to 202°C. The isotropization temperature of the polyacrylates increased with increasing the number of carbons of the methylenic spacer. The yield of the resulting polymer was changed by EB irradiation temperature from 4.5 to 41%. The highest yield was obtained when the monomer was polymerized in a liquid-crystalline phase. The same tendency was observed in the molecular weight of the resulting polymers. © 1994 John Wiley & Sons, Inc.     

2-(4-Biphenylyl)-1,3,4-oxadiazoles: synthesis and mesogenic studies

A series of 2-(4-biphenylyl)-1,3,4-oxadiazoles bearing alkyl or alkoxy substituents at the 4? position, and a hydrogen, or alkyl substituent (linear, branched, fluorinated or functionalised) at the 5 position were synthesised and characterised (51 compounds). Their mesogenic properties were evaluated using differential scanning calorimetry and polarising optical microscopy. Results show that substitution of the 1,3,4-oxadiazole ring for a terminal benzene ring in a conventional p-terphenyl enriched the mesogenic properties. Most of the new oxadiazole compounds exhibit either monotropic or enantiotropic smectic A mesophases with widths ranging from 3 to 50°C. A few compounds (short tailed) exhibit nematic phases and some compounds with branched or fluorinated alkyl substituents at the 5 position are also mesogenic.