Alexey Eremin

Polar bent-shape liquid crystals – from molecular bend to layer splay and chirality

Considerable progress has been achieved in understanding the fascinating structure and physical properties of the ferroelectric liquid crystalline phases formed by bent-core liquid crystals (BLC). In this review, we discuss a manifold of polar structures and phases found in BLCs such as orthogonal and tilted ferro-/antiferroelectric phases, smectic phases, switchable columnar phases, modulated structures and phases stabilised by a periodic lattice of defects such as dark conglomerate and nanofilament phases. We review the theoretical aspects of ferroelectricity in BLCs including existing microscopic theories and computer simulations, polarity and chirality phenomena. The last part of the paper is devoted to the peculiarities of the behavior of BLCs in a restricted geometry (freely suspended films and filament) and the perspective technological applications.

Spontaneous chiral ordering in the nematic phase of an achiral banana-shaped compound

A new achiral banana-shaped mesogen is presented which exhibits a nematic phase and an isotropic mesomorphic phase with spontaneous chiral ordering.

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.

Ferroelectric and antiferroelectric “banana phases” of new fluorinated five-ring bent-core mesogens

Two homologous achiral five-ring mesogens with lateral fluorine substituents on the core and on the outer rings are presented. Both compounds exhibit two B5 phases and the B2 phase. The high-temperature B5 phases possess an antiferroelectric ground state. The low-temperature B5 phase was found to be ferroelectric, which is indicated by the bistable switching. The assignment and characterization of the mesophases is based on XRD measurements, 1H-, 19F-, 13C-NMR and electro-optical measurements.

Ten isomeric five-ring bent-core mesogens: The influence of the direction of the carboxyl connecting groups on the mesophase behaviour

In order to study the role of the direction of the connecting groups in bent-core mesogens we synthesized two series of ten possible achiral isomeric five-ring bent-core compounds in which all aromatic rings are connected by ester groups and each of which possesses the same length of the terminal chains (octyloxy or dodecyloxy, respectively). The structure of the isomers is distinguished by the direction of at least one ester group, only. The mesophase behaviour of the compounds has been studied by polarizing microscopy, differential scanning calorimetry, X-ray experiments and electro-optical measurements. We have found that in spite of the minor structural differences a variety of mesophases occur (SmCPA, Colrec, Colob) whereby the clearing temperatures vary from 121 to 193 °C (octyloxy isomers) and 112 to 189 °C (dodecyloxy isomers). Depending on the direction of the ester groups some of these isomers show interesting properties, such as field-induced inversion of chirality in SmCPA and columnar phases, the field-induced enhancement of the clearing temperature, a second-order phase transition Colob n → SmCPA or the reversible field-induced phase transition Colob n → SmCPF. The unexpectedly strong influence of the direction of the connecting groups is discussed on the base of theoretical calculations and molecular dynamics simulation on isolated molecules.

Structural and conformational investigations in SmA and different SmC phases of new hockey stick-shaped compounds

New meta -substituted homologous three-ring mesogens, the 4-(3-n-decyloxyphenyliminomethyl) phenyl 4-n-alkyloxybenzoates, have been synthesized, which are non-linear due only to the attachment of one of the alkyloxy groups in a meta -position. The mesophases were studied by optical microscopy, differential scanning calorimetry, NMR spectroscopy, X-ray diffraction, and electro-optical and dielectric measurements. Unusual phase behaviour was observed on varying the length of the terminal chain. The most interesting finding is the occurrence of two polymorphic tilted smectic phases designated as SmC1 and SmC2. The existence of these phases was revealed by calorimetric studies and also from the pronounced difference in optical textures. It was shown from NMR measurements that the molecular orientation changes from a synclinic to an anticlinic arrangement in the SmC1 to SmC2 phase transition. It has also been shown, using NMR, that the SmC1 → SmC2 phase transition in these compounds is accompanied by a conformational change in the molecular fragment containing the aromatic ring with the meta-substituted terminal alkyloxy chain. This conformational change is linked to a change in the shape of the molecules and leads to a different packing of the molecules within the layers of the SmC2 phase. From dielectric measurements an increase by a factor of two was detected in the molecular mobility at the transition into the low temperature SmC2 phase. This finding supports a change in the packing as result of conformational changes.

1,2,4-oxadiazole-based bent-core liquid crystals with cybotactic nematic phases.

Several series of bent-core mesogens derived from 3,5-diphenyl-1,2,4-oxadiazole with or without lateral groups and with different length terminal chains at both ends, and polycatenar molecules with three to six alkoxy chains are synthesized and their mesomorphic behaviour is investigated by polarizing microscopy, differential scanning calorimetry, X-ray diffraction (XRD), dielectric, electro-optical and second-harmonic generation (SHG) experiments. Most compounds exhibit broad regions of skewed cybotactic nematic (NcybC ) and tilted smectic (SmC) phases with a strong tilt of the aromatic cores (up to 63°), but non-tilted SmA and NcybA phases are also observed for a compound that has only one terminal chain. The XRD patterns of the nematic phases of most of the compounds investigated indicate a 2D periodicity with short correlation length in the magnetically aligned samples. This is of importance for the general interpretation of the small-angle XRD splitting patterns typically observed for aligned samples of bent-core nematic phases. In most nematic phases one current peak is observed in the half period of an applied electric field, though no coherent signal is found in the SHG experiments. Based on additional electro-optical and dielectric results, the nematic phases are considered to be cybotactic nematic phases with local polar order, and show a dielectric reorientation of the polar domains. Only chiral nematic phases (NcybC *), but not blue phases, are obtained for compounds with one or two chiral (3S)-3,7-dimethyloctyloxy tail(s).

Structural characterization of the new polymorphic mesophases formed by bent-core molecules

A new achiral banana-shaped five-ring 2-methylresorcinol derivative fluorinated on the outer rings has been synthesized. This compound exhibits four antiferroelectric smectic phases characteristic for bent-core molecules (B2, B′2, B″2, B5). In addition, a highly viscous solid-like phase has been detected which also shows electro-optical switching. This is the first switchable highly ordered B phase. The characterization of the mesophases was made by X-ray diffraction, electro-optical measurements and dielectric spectroscopy.

Unexpected liquid crystalline behaviour of three-ring bent-core mesogens: bis(4-subst.-phenyl) 2-methyl-iso-phthalates

Three-ring bent-core bis(4-subst.-phenyl) 2-methyl-iso-phthalates exhibiting nematic, SmA and SmC phases are reported. The occurring mesophases have been identified by their optical textures and X-ray diffraction measurements which give also geometrical structural parameters like layer spacing and molecular tilt. Quantum chemical calculations on single molecules and X-ray structure analysis in the crystalline state indicate wide opening angles (about 155°) of the molecular legs due to the lateral methyl group in position 2 of the central phenyl ring. However solid state NMR spectroscopy in the liquid crystalline phases finds stronger molecular bending (bending angle to be about 138° in the SmA and about 146° in the nematic phase). Dielectric and SHG measurements give evidence that in the SmA phase a polar structure can be induced by application of an electric field which disappears in the isotropic liquid phase. The electric field not only leads to a slight textural change even in the SmA phase but also polar-type electric current response (PS about 200 nC cm−2) is observed. This unusual electro-optical behaviour is discussed on the basis of the orientation of polar clusters formed by the bent molecules. In the paper we not only attempt to characterize the mesophases and to describe their physical properties, but we also show that these types of molecules represent the borderline between bent-shaped and calamitic liquid crystals.

Paraelectric–antiferroelectric transitions in the bent-core liquid-crystalline materials

Ferroelectric liquid crystalline phases formed by achiral bent-core mesogens have been known for about seven years. However, only few materials have been found to exhibit both conventional nematic/smectic mesophases and “banana” phases, where steric packing of bent mesogens results in ferroelectric properties. In this paper we report some studies of such compounds showing transitions between paraelectric smectic A, smectic C and antiferroelectric smectic CP phases. Structure characterization as well as studies of ordering in mesophases have been performed with the help of a variety of experimental techniques including X-ray diffraction, NMR and dielectric spectroscopy as well as electrooptical measurements.