synthesis,phase transitions and optical properties of novel tetrathiafulvalene derivatives with extremely high molecular polarizabilities

The synthesis of novel unsymmetrically-substituted tetrathiafulvalene derivatives based on lithiation procedures is described. The disubstituted derivatives were synthesized as 1:1 cis/trans-isomeric mixtures, the compositions of which were established by ¹H NMR and ¹³C NMR spectroscopy. The transition temperatures, refractive indices, birefringence, polarizability and order parameter of each of the mixtures were determined and the values are discussed in comparison with analogous compounds with the tetrathiafulvalene unit replaced by a 1,4-phenylene group. In addition, we describe the synthesis of a number of monosubstituted tetrathiafulvalene derivatives and their associated thermal properties. The isomeric compounds presented in this paper have exceptionally large values of polarizability anisotropy, as compared with their phenyl-containing counterparts.     

Synthesis of O-Alkyl D-Xylitols with Potential Luquid-Crystalline Properties 1

Abstract

A general synthetic approach to enantiomerically pure x-O-alkyl-D-xylitols has been developed from D-xylose. These products provide access to new thermotropic liquid crystals.

     

An optically-active liquid-crystalline hexa-adduct of [60]fullerene which displays supramolecular helical organization

Polyaddition of mesogenic moieties to C60 were found to yield chiral supermolecular nanoparticles which exhibit iridescent helical chiral nematic phases.     

Effect of introducing thioether linkages on the molecular organization of chiral twin liquid crystals

Novel symmetric and non-symmetric chiral twin compounds possessing one or two thioether groups in a central spacer were prepared, and the effect of substituting oxygen for sulphur on the liquid crystalline properties investigated. Chiral twin compounds possessing an alkylsulphanyl spacer showed an antiferroelectric phase exclusively. However, replacing the alkyloxy chain of the analogous monomer by the alkylsulphanyl chain has no significant effect on the phase transition behaviour, i.e. both of the monomers showed the ferro- and ferri-electric phases as well as the antiferroelectric phase. Thus, different effects of introducing the thioether linkage were for the first time observed between twin and monomeric systems. The introduction of oxygen or sulphur atoms into the central alkyl spacer of the chiral twin was also investigated, and these modifications were found to stabilize the SmA phase. Furthermore, the twin compound possessing a thiaalkyl spacer showed two different molecular assemblies in the smectic A phase.     

Spontaneous formation of chiral macrostructures in achiral hockey-stick liquid crystals

We report the synthesis and properties of a homologous series of asymmetrically substituted 4-(5-(4-benzyloxyphenyl)-1,3,4-oxadiazol-2-yl)phenyl 2-X-4-dodecyloxybenzoates, which have pronounced hockey-stick molecular architectures. The structure was varied through the lateral substitution with various groups, X (H, Me, MeO, Cl, F) in the outer benzene ring. The effect of the lateral group on liquid crystal phase behaviour was investigated by thermal optical microscopy and differential scanning calorimetry. Nematic and dark conclomerate phases were observed with both displaying macroscopically chiral domains.     

Molecular complexity and the control of self-organising processes

In this article we investigate the complexity of the molecular architectures of liquid crystals based on rod-like mesogens. Starting from simple monomeric systems founded on fluoroterphenyls, we first examine the effects of aromatic core structure on mesophase formation from the viewpoint of allowable polar interactions, and then we model these interactions as a function of terminal aliphatic chain length. By incorporating a functional group at the end of one, or both, of the aliphatic chains we study the effects caused by intermolecular interfacial interactions in lamellar phases, and in particular the formation of synclinic or anticlinic modifications. We then develop these ideas with respect to dimers, trimers, tetramers, etc. We show, for dendritic systems, that at a certain level of molecular complexity the local mesogenic interactions become irrelevant, and it is gross molecular shape that determines mesophase stability. The outcome of these studies is to link the complexity of the molecular interactions at the nanoscale level, which lead to the creation of the various liquid-crystalline polymorphs, with the formation of mesophases that are dependent on complex shape dependencies for mesoscopic supermolecular architectures.     

The magnitude and temperature dependence of the Kerr constant in liquid crystal blue phases and the dark conglomerate phase

A new method of evaluating the Kerr constant in liquid crystals (LCs) is used to determine the temperature dependence of the Kerr effect in blue phases I and II (BPI and BPII) and to investigate the Kerr constant of the isotropic dark conglomerate (DC) phase. This method employs relatively small driving voltages and a vertical field switching (VFS) device geometry. An unusually large Kerr constant, K, is determined in the BPs of a non-polymer-stabilised material, ～3×10^?9 mV^?2 (BPI). The large value of K is attributed to significant pre-transitional values of the dielectric anisotropy and birefringence. K follows an inverse dependence on temperature and we consequently suggest that BPI demonstrates properties best suited to electro-optic devices. The new methodology has the advantage of revealing the dispersion of K in a single measurement. It is also possible to deconvolute the influence of the Kerr effect from measurements of electrostriction of the BP lattice. Finally, the Kerr effect has been measured for the first time in the DC phase of an oxadiazole bent-core liquid crystalline material, and is found to take rather low values, ～1×10^?11 mV^?2, which can be understood in the context of the physical properties of the material.     

Ferrielectric and antiferroelectric chiral twin liquid crystals showing a stable chiral nematic phase

A homologous series of chiral twin liquid crystals possessing identical chiral moieties at both peripheral ends, i.e. optically active α,ω -bis{4-[(4′-(1-methylheptyloxycarbonyl)-4-biphenylyl)oxycarbony]phenoxy}alkanes, has been prepared and their liquid crystalline properties investigated. The homologues preferred to show the ferrielectric and/or antiferroelectric phase rather than the ferroelectric phase. With ascending central spacer length, the temperature range of the ferrielectric phase became narrow and eventually disappeared for the dodecyl homologue, suggesting that the coupling in motion and/or direction between two mesogenic parts of each twin molecule has an important effect on the stabilization of the ferrielectric phase. The octyl and dodecyl homologues showed a wide temperature range chiral nematic phase (ca. 10°C or more), so that these compounds were found to be the first examples showing antiferroelectric and/or ferrielectric phases with a broad temperature range of the chiral nematic phase. X-ray diffraction studies showed that the homologues tend to form a mono-layered structure. The formation of a relatively well defined layered structure was also indicated, which is considered to be important for generating anticlinic ordering in the antiferroelectric and ferrielectric phases. An isotropic-isotropic transition characterized by the emergence of a broad diffuse DSC peak was observed for the even-membered homologues.     

Optical activity and light scattering in the isotropic and smectic A* phases of a highly chiral smectic liquid crystal

The results of optical activity measurements on the smectic A* phase of 1-methylheptyl 4'-[(4-n-tetradecyloxyphenyl)proprioloyloxy]biphenyl-4-carboxylate (14P1M7) and the chiral nematic phase of a chiral-racemic mixture of S-4-(2-methylbutyl)phenyl 4-decyloxybenzoate (CE6) are shown to be extremely similar. This is in full agreement with the proposed model of the A* phase as a twistgrain-boundary (TGB) phase. In addition, new light scattering measurements using circularly polarized light in a back-scattering geometry yield information on the fluctuations in the isotropic phase. Unlike in chiral nematics where only one structural mode is affected, the data show a strong deviation from the normal temperature dependence near the isotropic-smectic A* transition for two structural modes. Possible reasons for this behaviour in highly chiral smectic liquid crystals are discussed.