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See detailOn the balance between syn- and anticlinicity in smectic phases formed by achiral hockey-stick mesogens with and without chiral dopants
Enz, Eva; Findeisen-Tandel, Sonja; Dabrowski, Roman et al

in Journal of Materials Chemistry (2009), 19(19), 2950-2957

A series of achiral hockey-stick-shaped mesogens forming tilted smectic liquid crystal phases of synclinic SmC- as well as anticlinic SmCa-type was prepared and characterized. While all homologues exhibit ... [more ▼]

A series of achiral hockey-stick-shaped mesogens forming tilted smectic liquid crystal phases of synclinic SmC- as well as anticlinic SmCa-type was prepared and characterized. While all homologues exhibit both phases, the balance shifts from anticlinic to synclinic order upon elongation of the terminal chain at the meta-position, defining the hockey-stick shape. The elongation also leads to an increased kinetic hindrance of the transition between syn- and anticlinic phases and a decreased transition enthalpy. These observations indicate that a well-defined kink (short meta-substituted chain) promotes the anticlinic structure while a higher flexibility between kinked and rod-shape (long meta-substituted chain) promotes synclinic order. An intermediate chain-length homologue was selected as host material for doping with syn- and anticlinic rod-shaped chiral dopants, respectively, at varying concentrations. Opposite of what might be expected the balance between syn- and anticlinic order was not simply dictated by the choice of dopant. Instead, both types of tilting order prevailed with roughly the same strength as in the achiral host regardless of which chiral material was added, up to concentrations well beyond normal doping conditions. Thus, at least with hockey-stick-shaped achiral hosts, syn- as well as anticlinic chiral compounds can be used effectively as chiral dopants without necessarily having an important impact on the clinicity of the resulting mixture. The hockey-stick design concept should be useful in producing achiral anticlinic-forming mesogens for low-polarization, long-pitch antiferroelectric liquid crystal mixtures. Finally, we point out that a mixture study like the one carried out here yields a conclusive means of establishing the clinicity of achiral tilted smectics, an endeavour that can sometimes be far from trivial. [less ▲]

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See detailOn the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal
Lagerwall, Jan UL; Giesselmann, Frank; Saipa, Alexander et al

in Liquid Crystals (2004), 31(9), 1175-1184

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle ... [more ▼]

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A (SmA) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C (SmC) and smectic C-a (SmCa) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC phase, the distribution is biased such that the molecular tilt already present in SmA now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmCa is about 20degrees larger than in SmA. The large optical tilt (45degrees) in the SmCa phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations. [less ▲]

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