A state of matter in which molecules show a long-range orientational order and no positional order is called a nematic liquid crystal. The best known and most widely used (for example, in modern displays) is the uniaxial nematic, with the rod-like molecules aligned along a single axis, called the director. When the molecules are chiral, the director twists in space, drawing a right-angle helicoid and remaining perpendicular to the helix axis; the structure is called a chiral nematic. Here using transmission electron and optical microscopy, we experimentally demonstrate a new nematic order, formed by achiral molecules, in which the director follows an oblique helicoid, maintaining a constant oblique angle with the helix axis and experiencing twist and bend. The oblique helicoids have a nanoscale pitch. The new twist-bend nematic represents a structural link between the uniaxial nematic (no tilt) and a chiral nematic (helicoids with right-angle tilt).
Hydrocarbon linked mesogenic dimers are found to exhibit an additional nematic phase below the conventional uniaxial nematic phase as confirmed by x-ray diffraction. The phase produces unusual periodic stripe domains in planar cells. The stripes are found to be parallel to the rubbing direction (in rubbed cells) with a well-defined period equal to double the cell gap. The stripes appear without external electromagnetic field, temperature or thickness gradients, rubbing or hybrid alignment treatments. Simple modeling proposes a negative sign for at least one of the two elastic constants: splay and twist, as a necessary condition for the observed pattern.
Infrared absorbance measurements have been carried out on two liquid crystalline organo-siloxane tetrapodes. Results unambiguously show the existence of a biaxial nematic phase below a uniaxial nematic phase. The three components of IR absorbance are used to calculate the various order parameters. On cooling, a weak first-order transition from isotropic to nematic is observed, followed by a second-order phase transition to biaxial nematic where the biaxiality parameters are found to be significantly large. Results are supported by observations from conoscopy and texture. Temperature dependences of the order parameters are well explained by the mean-field model for a biaxial phase.
The term liquid crystal is often associated with fascinating compounds that exhibit unusual melting or solubilisation properties, however, it also represents a unique collection of mesophases that exist between the solid state and the amorphous liquid. As such, this unique state of matter can be accessed by a wide variety of materials from low molar mass to polymeric systems. In this Feature Article we describe some recent studies concerning the liquid-crystalline behaviour of ‘in-between’ materials that have discrete molecular structures, and which are oligomeric but not low molar mass or polymeric systems. Thus, these materials could be described as having supermolecular architectures. We examine some of their mesophase properties and their abilities to form supramolecular assemblies. The development of liquid crystals that have large molecular structures or consist of large scale assemblies is one step towards creating novel self-organising systems which are of a similar dimension to certain biological materials, such as proteins.
27 September 2006 in Journal of the American Chemical Society