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.     

First observation of double-twisted helical structure in a banana-shaped achiral molecule

The double-twisted helical structure was confirmed for the first time for the smectic phase of a banana-shaped molecular system from observation of the microscopic pattern. Optically polarized microscopic textures and phase transitions of 1,3-phenylene bis\[4-(3-chloro-4- n-octyloxyphenyliminomethyl) benzoate (PBCOB) and related compounds are described. The chloro-substituent introduced into the 3-position of the Schiff's base moiety of the banana-shaped molecule destabilized the smectic phase and enhanced new mesomorphic properties. The mesophases exhibited by the octyloxy homologue of the chloro-substituted compound were of the smectic phases, SmX1 and SmX2. The mixing behaviour between chloro-substituted and non-chloro-substituted compounds resulted in the appearance of a wide miscibility gap and enlargement of the SmX1 phase which can be seen in a lateral chloro-substituted compound.     

First observation of double-twisted helical structure in a banana-shaped achiral molecule

The double-twisted helical structure was confirmed for the first time for the smectic phase of a banana-shaped molecular system from observation of the microscopic pattern. Optically polarized microscopic textures and phase transitions of 1,3-phenylene bis\[4-(3-chloro-4- n-octyloxyphenyliminomethyl) benzoate (PBCOB) and related compounds are described. The chloro-substituent introduced into the 3-position of the Schiff's base moiety of the banana-shaped molecule destabilized the smectic phase and enhanced new mesomorphic properties. The mesophases exhibited by the octyloxy homologue of the chloro-substituted compound were of the smectic phases, SmX1 and SmX2. The mixing behaviour between chloro-substituted and non-chloro-substituted compounds resulted in the appearance of a wide miscibility gap and enlargement of the SmX1 phase which can be seen in a lateral chloro-substituted compound.     

Ferroelectric liquid crystals from banana-shaped achiral molecules with vinyl end groups

Banana-shaped achiral compounds, the 1,3-phenylene bis[4-(alkenyloxyphenyliminomethyl)benzoate]s, were synthesized with varying length of the alkenyl group; their ferroelectric properties are described. The smectic mesophases, including a switchable chiral smectic C (SmC*) phase, were characterized by differential scanning calorimetry, polarizing optical microscopy and the triangular wave method. The presence of vinyl groups at the ends of the linear side-wings in the banana-shaped achiral molecules, containing a Schiff's base mesogen, induced a decrease in melting temperature and formation of the switchable SmC* phase in the melt. The compound having the octenyloxy group exhibited a spontaneous polarization of 120 nC cm^?2 on reversal of an applied electric field.     

Ferroelectric liquid crystals from banana-shaped achiral molecules with vinyl end groups

Banana-shaped achiral compounds, the 1,3-phenylene bis[4-(alkenyloxyphenyliminomethyl)benzoate]s, were synthesized with varying length of the alkenyl group; their ferroelectric properties are described. The smectic mesophases, including a switchable chiral smectic C (SmC*) phase, were characterized by differential scanning calorimetry, polarizing optical microscopy and the triangular wave method. The presence of vinyl groups at the ends of the linear side-wings in the banana-shaped achiral molecules, containing a Schiff's base mesogen, induced a decrease in melting temperature and formation of the switchable SmC* phase in the melt. The compound having the octenyloxy group exhibited a spontaneous polarization of 120 nC cm^-2 on reversal of an applied electric field.     

Liquid crystal phases of achiral banana-shaped molecules: a computer simulation study

The phase behaviour of achiral banana-shaped molecules was studied by computer simulation. The banana-shaped molecules were described by model intermolecular interactions based on the Gay-Berne potential. The characteristic molecular structure was considered by joining two calamitic Gay-Berne particles through a bond to form a biaxial molecule of point symmetry group C 2v with a suitable bending angle. The dependence on temperature of systems of N =1024 rigid banana-shaped molecules with bending angle ϕ=140° has been studied by means of Monte Carlo simulations in the isobaric-isothermal ensemble ( NpT ). On cooling an isotropic system, two phase transitions characterized by phase transition enthalpy, entropy and relative volume change have been observed. For the first time by computer simulation of a many-particle system of banana-shaped molecules, at low temperature an untilted smectic phase showing a global phase biaxiality and a spontaneous local polarization in the layers, i.e. a local polar arrangement of the steric dipoles, with an antiferroelectric-like superstructure could be proven, a phase structure which recently has been discovered experimentally. Additionally, at intermediate temperature a nematic-like phase has been proved, whereas close to the transition to the smectic phase hints of a spontaneous achiral symmetry breaking have been determined. Here, in the absence of a layered structure a helical superstructure has been formed. All phases have been characterized by visual representations of selected configurations, scalar and pseudoscalar correlation functions, and order parameters.     

Ferroelectric smectic meso-phase formed by banana-shaped achiral liquid crystals

A new banana-shaped achiral molecule, 1,3-phenylene bis[4-(3-chloro-4-n-octyloxyphenyliminomethyl)benzoate] (PBCOB) has been synthesized, and its ferroelectric properties and homeotropic alignment investigated. The presence of a lateral chloro-substituent in the Schiff 's base moiety prevents the regular stacking of molecules and results in lowering the transition temperature and the degree of crystallinity of the switchable banana phase. Their smectic mesophases, including a switchable banana phase B₇, were characterized by differential scanning calorimetry, X-ray scattering and polarizing optical microscopy. Both the left- and right-handed helical domains are spontaneously formed upon cooling from the isotropic liquid to the switchable banana phase B₇. By X-ray study, the smectic phases showed a layer spacing of 38.1 Å, compatible with the end-to-end distance of the molecule with a bent conformation. Significantly, the smectic B7 phase exhibited a periodicity of 292 Å that corresponds to a helical structure with periodicity about 7.5 times 38.1 Å. The spontaneous polarization for PBCOB is about 50 nCcm^-2 and shows a temperature dependence. The ferroelectric lyomesophase of PBCOB showed a ferroelectric electro-optical switching range extending more than 50°C, switchable at room temperature.     

Novel sulphur-containing banana-shaped liquid crystal molecules

In this preliminary report we present the mesomorphic properties and electro-optic investigations of three new 'banana-shaped' mesogens. The materials are structurally similar to Niori's the original bent-core materials but possess alkylthio substituents in place of alkoxy substituents. Microscopic investigations revealed an unusual 'spiral-domain texture', similar to that observed in the 'B₇' phase of related materials. Further investigations support our earlier observations that the materials display antiferroelectric switching in this phase, in two of the new materials studied. The nature of this phase, in comparison with the 'switchable' (B₂) and 'chiral-domain' (B₄) phases of the original materials, is discussed.     

Novel sulphur-containing banana-shaped liquid crystal molecules

In this preliminary report we present the mesomorphic properties and electro-optic investigations of three new 'banana-shaped' mesogens. The materials are structurally similar to Niori's the original bent-core materials but possess alkylthio substituents in place of alkoxy substituents. Microscopic investigations revealed an unusual 'spiral-domain texture', similar to that observed in the 'B₇' phase of related materials. Further investigations support our earlier observations that the materials display antiferroelectric switching in this phase, in two of the new materials studied. The nature of this phase, in comparison with the 'switchable' (B₂) and 'chiral-domain' (B₄) phases of the original materials, is discussed.     

Synthesis and characterization of achiral banana-shaped liquid crystalline molecules containing bisnaphthyl moieties

Three analogous series of symmetric banana-shaped liquid crystalline molecules containing bisnaphthyl units were synthesized and characterized. The effects of linking groups (on the side wings) and lateral meta-fluoro substitutions (on the middle outer rings) on the mesogenic properties were examined. The type of mesophase depends on the lengths of terminal alkoxy chains. Thus, achiral molecules with shorter flexible chains (n = 8) exhibit a rectangular columnar (B₁) phase, while analogous derivatives with longer flexible chains (n = 12) display the B₂ phase. All lateral meta-fluoro substituted analogues (series II) possess the lowest isotropization temperatures and the narrowest mesophasic ranges of the B₁ and B₂ phases. The B₁ and B₂ phases were confirmed by X-ray diffraction, polarizing optical microscopy (POM) and electro-optical (EO) switching experiments. An electric field-induced transition from an antiferroelectric (tristable) state to a ferroelectric (bistable) state was observed in the EO measurements. Spontaneous polarization (by switching current response), tilt angle of chiral domains (by POM), and transmittance-voltage measurements of the B₂ phase in related compounds have been surveyed in this study.     

Mesomorphic properties of achiral halogen-substituted banana-shaped compounds

Three banana-shaped achiral compounds, derivatives of 4,6-dichloro-1,3-phenylene bis-[4-(4- n -octyloxyphenyliminomethyl) benzoate], were synthesized by varying the substituent ( X =H, F and Cl). Their mesomorphic properties were investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray analysis. The compound with X = H exhibited an enantiomeric nematic phase. The compounds with X = F and Cl formed a nematic phase on heating, while on cooling they formed a nematic phase at high temperature and a smectic A phase at a lower temperature (monotropic). A schematic representation of the mesophase structures for the compound with X = F is also illustrated.     

Mesomorphic properties of achiral halogen-substituted banana-shaped compounds

Three banana-shaped achiral compounds, derivatives of 4,6-dichloro-1,3-phenylene bis-[4-(4-n-octyloxyphenyliminomethyl) benzoate], were synthesized by varying the substituent (X = H, F and Cl). Their mesomorphic properties were investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray analysis. The compound with X = H exhibited an enantiomeric nematic phase. The compounds with X = F and Cl formed a nematic phase on heating, while on cooling they formed a nematic phase at high temperature and a smectic A phase at a lower temperature (monotropic). A schematic representation of the mesophase structures for the compound with X = F is also illustrated.     

Antiferroelectric behaviour of achiral mesogenic polymer mixtures

X-ray structure determination and pyroelectric and piezoelectric measurements have been carried out on mesogenic mixtures composed of achiral side chain polymers and their monomers. Certain mixtures show antiferroelectric polarization hysteresis loops in the mesophase which was shown to be a bilayered smectic C, while the two components of the mixtures taken alone show no antiferroelectricity. The results obtained on the polymer-monomer mixtures are interpreted in terms of the smectic C structure with alternating tilt which, from a symmetry viewpoint, is allowed to be antiferroelectric. The antiferroelectric mixtures, on being cooled to the glassy state under a d.c. electric field applied, reveal high pyroelectric coefficients with prospects for application as IR detectors.     

Synthesis and liquid crystal properties of new banana-shaped cinnamoyl derivatives

Three new achiral five-ring banana-shaped homologous series have been synthesized and their liquid crystalline properties studied by polarizing microscopy, differential scanning calorimetry, and electro-otpical analysis. The compounds consist of two identical mesogenic structures of bis (alkoxycinnamoyloxybenzoates) linked on a different central ring (unsubstituted or methyl-substituted). The length of the terminal alkoxy groups was varied from heptyloxy to dodecyloxy; the hexadecyloxy group was also included in the study. It was found that the polymorphism of compounds can be strongly dependent upon molecular structure in this class of compound. In particular, substituents on the central ring may exert a significant effect on the type of mesophase observed.     

Two-dimensional assemblies of banana-shaped liquid crystal molecules on HOPG surface

Two-dimensional assemblies of a series of banana-shaped liquid crystal molecules, 1,3-phenylene bis[4-(4-n-alkylphenyliminomethyl) benzoates] (P-n-PIMB, n = 12, 14, 18), are investigated on a highly oriented pyrolytic graphite (HOPG) surface by using scanning tunneling microscopy (STM) at a submolecular level in an ambient environment. Two types of molecular arrangements are observed in these self-assemblies with different stripe widths that resulted from the organization of the alkyl chains. The polarization of the P-n-PIMB monolayers is exactly compensated by the adjacent lamellae with opposite bent direction. Furthermore, a bilayer structure is found in the assembly of P-18-PIMB molecules. In comparison with a gemini surfactant molecule, 4,4'-di[4-(octadecylmethylamino)styryl]-1,1'-pentamethylenebispyridinium dibromide (OPD), P-n-PIMB molecules appear in more complicated packing arrangements. The results in this paper demonstrate the effects of the molecular structures on the adlayer arrangement and will be helpful in fabricating two-dimensional molecular structures on solid surfaces.     

Synthesis and liquid crystal properties of new banana-shaped cinnamoyl derivatives

Three new achiral five-ring banana-shaped homologous series have been synthesized and their liquid crystalline properties studied by polarizing microscopy, differential scanning calorimetry, and electro-otpical analysis. The compounds consist of two identical mesogenic structures of bis (alkoxycinnamoyloxybenzoates) linked on a different central ring (unsubstituted or methyl-substituted). The length of the terminal alkoxy groups was varied from heptyloxy to dodecyloxy; the hexadecyloxy group was also included in the study. It was found that the polymorphism of compounds can be strongly dependent upon molecular structure in this class of compound. In particular, substituents on the central ring may exert a significant effect on the type of mesophase observed.     

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.     

Electro-disclinic effect in tilted smectic phases of banana-shaped liquid crystal materials

We give the first evidence that the director tilt angle can be reduced by electric fields in the tilted smectic phase of banana-shaped molecules. In these phases the value of polarization is determined by the molecular packing and no electro-clinic effect is expected. Our studies show that high electric fields eventually induce a meta-stable phase with zero director tilt. The tilted phase slowly recovers at low fields. We propose that the field-induced quenching of the layer fluctuations is responsible for the observed effects.     

Electro-disclinic effect in tilted smectic phases of banana-shaped liquid crystal materials

We give the first evidence that the director tilt angle can be reduced by electric fields in the tilted smectic phase of banana-shaped molecules. In these phases the value of polarization is determined by the molecular packing and no electro-clinic effect is expected. Our studies show that high electric fields eventually induce a meta-stable phase with zero director tilt. The tilted phase slowly recovers at low fields. We propose that the field-induced quenching of the layer fluctuations is responsible for the observed effects.