A chiral induced ferroelectric liquid crystal phase transition with a vanishingly small enthalpy

Information on molecular interactions that give rise to the stabilization of various ferroelectric, liquid-crystalline mesophases is important to the realization of their potential utility in a wide variety of optical devices. Understanding the roles that optical activity and optical purity play in the formation and properties of the various smectic phases is therefore of particular interest. In order to study this relationship three new liquid-crystalline materials were prepared, one as a racemic mixture, the other two as the optically active analogues. The optically active isomers appear to exhibit a different mesophase morphology from the racemate. The chiral compounds apparently possess two extra ferroelectric mesophases in comparison to the racemic mixture. The transitions to and from these phases have extremely small enthalpies. An attempt is made to explain the results for the chiral compounds in terms of differing dipolar couplings in the chiral ferroelectric phases. In the racemic mixture these interactions are compromised or scrambled by a loss of asymmetry thus destabilizing these extra phases.     

Twisted smectic A phases in side chain liquid crystal polymers

Abstract

The syntheses of two side chain liquid crystal polymers, a polyacrylate and a polymethacrylate, are reported. In each of the polymers the liquid-crystalline side group carries an asymmetric carbon atom, thereby making some of the liquid crystal phases formed by the polymers optically active and chiral. For the chiral polyacrylate smectic A and chiral ferroelectric smectic C phases are observed, however for the chiral polymethacrylate a cholesteric phase is detected above the smectic A phase. It is found that the smectic A to cholesteric phase transition is mediated by the formation of an intermediary twisted smectic A phase. This intermediary phase is a liquid-crystalline analogue of the Abrikosov flux phase found in Type II superconductors.     

Synthesis and properties of new ferroelectric liquid-crystalline compounds having a tolane rigid core and an optically active alkyl sulphinate group

Abstract

The synthesis and the properties of new ferroelectric liquid-crystalline compounds with a tolane rigid core and an optically active alkyl sulphinate group are reported. These compounds contain two chiral centres: a sulphinate group and a branched aliphatic chain. The two pure diastereomers having opposite configurations on the sulphur have been isolated. The mesomorphic behaviour of these two compounds is different, only one exhibiting an enantiotropic chiral smectic C phase; this clearly demonstrates the role of the sulphur configuration in determining the thermotropic properties. The mesomorphic transition temperatures, the structural behaviour as a function of temperature and preliminary measurements of the spontaneous polarization are presented.     

Chirality in liquid crystals. The remarkable phenylpropiolates

The biphenylyl esters of the 4-n-alkoxyphenylpropiolic acids are a unique family of liquid-crystalline materials. In particular, when the biphenyl moiety of the compounds carries a chiral end-group, many optically active mesophases are created which exhibit unusual structures and physical properties. For instance, when the chiral group attached to the biphenyl moiety is 1-methylheptyl then Abrikosov, twist grain boundary smectic A* and antiferroelectric smectic C* phases are observed. The wide variety of chiral phases and electrochiral properties exhibited by this family of materials makes them ideal candidates for exploring chirality in the liquid-crystalline state. These investigations allow us to contrast and compare chirality dependent phenomena in liquid crystals, thereby producing a broader view of the concept of chirality in organized fluids than is traditionally presented.     

Twisted smectic A phases in side chain liquid crystal polymers

The syntheses of two side chain liquid crystal polymers, a polyacrylate and a polymethacrylate, are reported. In each of the polymers the liquid-crystalline side group carries an asymmetric carbon atom, thereby making some of the liquid crystal phases formed by the polymers optically active and chiral. For the chiral polyacrylate smectic A and chiral ferroelectric smectic C phases are observed, however for the chiral polymethacrylate a cholesteric phase is detected above the smectic A phase. It is found that the smectic A to cholesteric phase transition is mediated by the formation of an intermediary twisted smectic A phase. This intermediary phase is a liquid-crystalline analogue of the Abrikosov flux phase found in Type II superconductors.     

Thermal analysis of binary liquid crystalline mixtures

Two series of binary mixtures composed of bent shaped and rod like molecules are reported. The first star shaped bent core molecules were synthesized and used as a component of binary mixtures. The chiral rod like compounds having commensurable length with the arms of the bent core compounds have been chosen for these mixtures. The resulted compositions show various thermotropic liquid crystalline phases that are characteristic to both types of liquid crystalline materials. In case of mixing the rod like molecules to the bent core compound the B2, B7 and induced B1 phases have been observed. While using the star-shaped bent core and chiral rod like compounds in mixture, the paraelectric smectic A, ferroelectric smectic C* and orthogonal hexatic smectic B phases were preferred. The appearing mesophases were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction methods.     

Synthesis and properties of new ferroelectric liquid-crystalline compounds having a tolane rigid core and an optically active alkyl sulphinate group

The synthesis and the properties of new ferroelectric liquid-crystalline compounds with a tolane rigid core and an optically active alkyl sulphinate group are reported. These compounds contain two chiral centres: a sulphinate group and a branched aliphatic chain. The two pure diastereomers having opposite configurations on the sulphur have been isolated. The mesomorphic behaviour of these two compounds is different, only one exhibiting an enantiotropic chiral smectic C phase; this clearly demonstrates the role of the sulphur configuration in determining the thermotropic properties. The mesomorphic transition temperatures, the structural behaviour as a function of temperature and preliminary measurements of the spontaneous polarization are presented.     

Low frequency dielectric spectroscopy on mixtures containing ferroelectric liquid crystals

Abstract

Dielectric spectroscopy (frequency range 10 ^?1 Hz to 10⁵ Hz, temperature range 300 K to 370 K) was employed to investigate the Goldstone mode in ferroelectric liquid-crystalline mixtures of chiral and achiral compounds. While the spontaneous polarization decreases with increasing fraction of the achiral molecules the Goldstone mode remains constant in its oscillatory strength. As expected the Goldstone mode frequency shifts to lower values with increasing amount of achiral molecules in the ferroelectric liquid-crystalline mixture.     

Dark conglomerate phases of bent-core liquid crystals

ABSTRACT

Spontaneous or induced chiral symmetry breaking in achiral systems is unusual and understanding the origin of such a phenomenon has been an important area of research for several years. The optically isotropic mesophases exhibited by unconventional liquid crystals are one of the most interesting systems to investigate spontaneous chiral symmetry breaking in liquid crystal mesophases formed by achiral moieties. The dark conglomerate (DC) phases are one such optically isotropic family of phases. In this paper, a detailed account of the tendency of bent-core mesogens to form a variety of polar smectic phases, the formation of DC phases due to layers deformations and the general optical, electrical, physical properties of the DC phases are given. An example of a DC phase which exhibit distinct electro-optic properties is described with the nature of dynamics of the response and physical reasons responsible for such behaviour. The challenges and prospects of the DC phases are discussed for their potential applications in novel devices.     

Silicon-containing polyphilic bent-core molecules: the importance of nanosegregation for the development of chirality and polar order in liquid crystalline phases formed by achiral molecules

Polyphilic molecules composed of a bent aromatic core, oligo(siloxane) units, and alkyl segments were synthesized, and the self-organization of these molecules was investigated. Most materials organize into polar smectic liquid crystalline phases. The switching process of these mesophases changes from antiferroelectric for the nonsilylated compounds via superparaelectric to surface-stabilized ferroelectric with increasing segregation of the silylated segments. It is proposed that the siloxane sublayers stabilize a polar synclinic ferroelectric (SmC(s)P(F)) structure, and the escape from a macroscopic polar order as well as steric effects leads to a deformation of the layers with formation of disordered microdomains, giving rise to optical isotropy. Another striking feature is the spontaneous formation of chiral domains with opposite handedness. For two compounds, a temperature-dependent inversion of the optical rotation of these domains was found, and this is associated with an increase of the tilt angle of the molecules from < 45 degrees to > 50 degrees. This observation confirms the recently proposed concept of layer optical chirality (Hough, L. E.; Clark, N. A. Phys. Rev. Lett. 2005, 95, 107802), which is a new source of optical activity in supramolecular systems. With increasing length of the alkyl chains, segregation is lost and a transition from smectic to a columnar phase is found. In the columnar phase, the switching process is antiferroelectric and takes place by rotation of the molecules around the long axes, which reverses the layer chirality; that is, the racemic ground-state structure is switched into a homogeneous chiral structure upon application of an electric field.     

Diasteredmeric Alkylphenylphdsphinic Acids Derivatives Containing Menthyl,Thionedmenthyl and Aminomenthyl Groups: Synthesis,Chirality and Applications

Abstract

Recently we have found¹ that the condensation of racemic alkylphenylphosphinochloridite with menthol affords a mixture of diastereomers. We have also demonstrated utility of this reaction f o r the synthesis of optically active phosphines and amides^1,2.

In this communication we present application of neomenthanethiol and menthaneamine as chiral auxiliaries inducing optical activity at the phosphorus atom.     

Nanostructured assemblies of liquid-crystalline supermolecules: from display to medicine

ABSTRACT

Liquid crystal oligomers have a supermolecular structure in which two or more mesogenic units are interconnected through flexible spacers. They can form various molecular packing structures in their liquid-crystalline phases. We present flexible LC oligomers stabilising optically isotropic phases, i.e. blue phases (BPs) and chiral conglomerate phases. Hysteresis free switching, high contrast and wide viewing angle are obtainable in the amorphous BPIII without surface treatment. Spontaneous mirror symmetry breaking in layered phases of achiral flexible linear trimers produces periodic nanostructured surfaces. Then we demonstrate the effects of liquid-crystallinity on anticancer activities. Biological systems have links with liquid crystallinity. We found a molecular assembly of mesogenic molecules possessing an active site as a novel therapeutic approach against solid cancer cells.     

Synthesis and properties of new ferroelectric liquid crystalline compounds having a 1, 2-diphenylethane structure

Abstract

Chiral 1, 2-diphenylethane derivatives have been synthesized and found to form stable chiral Sc phases exhibiting ferroelectric properties. Comparison with diphenylacetylene derivatives revealed that flexibility of the bridging groups between two benzene nuclei strongly influences the stability of mesophases as well as transition temperatures.     

Synthesis and Stereochemistry of Optically Active Selenium and Tellurium Compounds

Abstract

The synthesis and stereochemistry of tricoordinated optically active selenium and tellurium compounds are described. Telluronium salts, telluronium imides, and seleninic acids were prepared and optically resolved by fractional recrystallization of diastereomeric mixtures or by chromatography using a chiral column of racemic mixtures. Diphenyl dichalcogenides also were optically resolved by chiral crystallization. Their absolute configurations were determined or estimated based on X-ray crystallographic analysis, specific rotations, and circular dichroism spectra. The kinetic studies and the mechanism for the racemization were also studied.     

Structural characterization of organosiloxane liquid crystals with a transverse or longitudinal dipole

In this work we report the characterization of two organosiloxane liquid crystalline compounds by means of DSC, polarizing optical microscopy and X-ray diffraction. These compounds can be used for dye guest-host ferroelectric displays. We focus this investigation on the molecular organization of the SmC phases of the two pure compounds to help elucidate the physical behaviour of mixtures with different concentrations of the dye and the guest host. The existence of longitudinal and transverse dipoles in the molecules of the dye and the chiral guest-host respectively are responsible for the different molecular organizations in the SmC mesophases of each compound. Taking into account the experimental results and the complexity of the molecules, we present coherent models to explain the molecular arrangements in the mesophases of both compounds.     

Structural characterization of organosiloxane liquid crystals with a transverse or longitudinal dipole

In this work we report the characterization of two organosiloxane liquid crystalline compounds by means of DSC, polarizing optical microscopy and X-ray diffraction. These compounds can be used for dye guest-host ferroelectric displays. We focus this investigation on the molecular organization of the SmC phases of the two pure compounds to help elucidate the physical behaviour of mixtures with different concentrations of the dye and the guest host. The existence of longitudinal and transverse dipoles in the molecules of the dye and the chiral guest-host respectively are responsible for the different molecular organizations in the SmC mesophases of each compound. Taking into account the experimental results and the complexity of the molecules, we present coherent models to explain the molecular arrangements in the mesophases of both compounds.     

4-(5-Alkyl-2-pyridinyl)phenyl alkanoates: Some novel smectic materials for display devices

Abstract

Three homologous series of 4-(5-alkyl-2-pyridinyl)phenyl alkanoates have been prepared. The synthesis and the liquid crystal transition temperatures of these esters are reported. Many members of these three ester series exhibit enantiotropic, wide range smectic F mesophases and some narrow range smectic C mesophases. However, in admixture with a chiral smectic C base mixture, the esters often induce a substantial increase in the chiral smectic C–smectic A transition temperature and, at the same time, decrease the temperature of crystallization. Thus, the temperature range of the chiral smectic C mesophase is substantially extended at both high and low temperatures. Ordered smectic mesophases are only observed at very low temperatures, if at all. These chiral smectic C mixtures are characterized by short switching times in surface-stabilized ferroelectric liquid crystal displays (SSFLCD). These novel esters are of especial interest for short-pitch chiral smectic C mixtures for short pitch bistable ferroelectric liquid crystal displays (SBFLCD) with short response times.     

Stable frustrated phases in chiral liquid crystals derived from optically active (R)- and (S)-3-ethylmercapto-2-methylpropionic acids

Highly optically pure (R)- and (S)-3-ethylmercapto-2-methylpropionic acids were synthesized by using optically active (D)- and (L)-2,10-camphorsultams as chiral auxiliaries, respectively. Their derivatives, (R)- and (S)-EMMPNmB (m=6-12), were prepared for investigation. Microscopic texture observations demonstrated that the materials possess three stable frustrated phases: BP, TGB_A* and TGB_C* phases. Interestingly, it was found that the N* phase behaves as an intermediary phase between BP and TGB_A* phases in a rather narrow temperature range (calc. 0.5-1.4°C). A study of the racemic mixture, (±)-EMMPNmB (m=10), indicated that the chirality of the molecule could suppress the formation of smectic phases in the heating process. An increase of alkyl chain length favoured the formation of the TGB phases particularly, in accompaniment with a change of TGB phases from monotropic to enantiotropic. Moderate maximum P _S values (calc. 14-19 nC cm^-2) and apparent tilt angle (calc. 20°) were obtained for the TGB_C* phase in a surface stabilized ferroelectric liquid crystal geometry.     

Thiophene-based bent-shaped luminescent liquid crystals: synthesis and characterisation

Five new bent-shaped compounds based on the 2,5-disubstituted thiophene central core were successfully synthesised. The lengths of the rigid centres as well as the degree of conjugation were varied by coupling benzene, naphthalene and biphenyl systems to the thiophene through Sonogashira cross-coupling. The thermal, mesomorphic and optical properties of these variants were determined. Compounds 5a,b and 8a displayed liquid-crystalline smectic and nematic mesophases. Strong blue fluorescence was observed for the final compounds.     

Optically Biaxial,Re‐entrant and Frustrated Mesophases in Chiral,Non‐symmetric Liquid Crystal Dimers and Binary Mixtures

Sixteen optically active, non‐symmetric dimers, in which cyanobiphenyl and salicylaldimine mesogens are interlinked by a flexible spacer, were synthesized and characterized. While the terminal chiral tail, in the form of either (R)‐2‐octyloxy or (S)‐2‐octyloxy chain attached to salicylaldimine core, was held constant, the number of methylene units in the spacer was varied from 3 to 10 affording eight pairs of (R & S) enantiomers. They were probed for their thermal properties with the aid of orthoscopy, conoscopy, differential scanning calorimetry and X‐ray powder diffraction. In addition, the binary mixture study was carried out using chiral and achiral dimers with the intensions of stabilizing optically biaxial phase/s, re‐entrant phases and important phase sequences. Notably, one of the chiral dimers as well as some mixtures exhibited a biaxial smectic A (SmA_b) phase appearing between a uniaxial SmA and a re‐entrant uniaxial SmA phases. The mesophases such as chiral nematic (N*) and frustrated phases viz., blue phases (BPs) and twist grain boundary (TGB) phases, were also found to occur in most of the dimers and mixtures. X‐ray diffraction studies revealed that the dimers possessing oxybutoxy and oxypentoxy spacers show interdigitated (SmA_d) phase where smectic periodicity is over 1.4 times the molecular length; whereas in the intercalated SmA (SmA_c) phase formed by a dimer having oxydecoxy spacer the periodicity was found to be approximately half the molecular length. The handedness of the helical structure of the N* phases formed by two enantiomers was examined with the aid of CD measurements; as expected, these enantiomers showed optical activities of equal magnitudes but with opposite signs. Overall, it appears that the chiral dimers and mixtures presented herein may serve as model systems in design and developing novel materials exhibiting the apolar SmA_b phase possessing D_2h symmetry and nematic‐type biaxiality.