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).

The underlying theme of this Critical Review is the relationship between molecular structure and liquid crystalline behaviour in a class of materials referred to as liquid crystal oligomers. For the purposes of this review, a liquid crystal oligomer will be defined as consisting of molecules composed of semi-rigid mesogenic units connected via flexible spacers. Much of the review will be devoted to structure–property relationships in the simplest oligomers, namely dimers, in which just two mesogenic units are connected by a single spacer. Along the way we will see how this molecular architecture has been exploited to address issues in a range of quite different areas and has given rise to potential applications for these materials. On the whole, only compounds in which the mesogenic units are linked essentially in a linear fashion will be considered while structures such as liquid crystal dendrimers and tetrapodes fall outside the scope of this review. The review will be of interest not only to scientists working directly in this area but in particular to those interested in understanding the relationships between structure and properties in polymers, and those designing materials for new applications (231 references).

Electrical tuning of selective reflection of light is achieved in a very broad spectral range from ultraviolet to visible and infrared by an oblique helicoidal state of a cholesteric liquid crystal in a wide temperature range (including room temperature). The phenomenon offers potential applications in tunable smart windows, lasers, optical filters and limiters, as well as in displays.

This review focuses on structure-property relationships in liquid crystal oligomers, which consist of molecules containing two or more mesogenic units linked via flexible spacers essentially in a linear fashion and so does not consider, for example, liquid crystal dendrimers and tetrapodes. Previous reviews have tended to focus mainly on liquid crystal dimers in which just two mesogenic units are interconnected by a single spacer. By contrast, this review is largely devoted to higher oligomers such as liquid crystal trimers and tetramers containing three or four mesogenic units connected by two or three spacers, respectively.

The transitional properties of three methylene-linked liquid crystal dimers are reported, namely, 1,5-bis(4-cyanoanilinebenzylidene-4′-yl)pentane (CN-5-CN), 1,5-bis(4-methoxyanilinebenzylidene-4′-yl)pentane (1O-5-O1), and 1,5-bis(4-ethoxyanilinebenzylidene-4′-yl)pentane (2O-5-O2). Each dimer exhibits two monotropic mesophases. The higher temperature mesophase is a normal nematic phase while the lower temperature phase is assigned as a twist-bend nematic phase. The assignment of the twist-bend nematic phase was based on the strong similarities in the optical textures observed to those reported recently for a structurally similar dimer. The complete miscibility of the mesophases exhibited by CN-5-CN and 1O-5-O1 has been established. The analogous hexamethylene-linked dimers exhibit only the normal nematic phase as do the corresponding ether-linked dimers. A review of the literature reveals another five methylene-linked odd-membered dimers that exhibit a nematic–nematic transition and, in each, the lower temperature nematic phase exhibits similar properties to those reported for the twist-bend nematic phase. The formation of this new nematic phase has been attributed to a negative bend elastic constant which results from the bent geometry of methylene-linked odd-membered dimers.

Six series of a family of non-symmetric dimers, the α-(4-cyanobiphenyl-4′-yloxy)-ω-(4-n-alkylanilinebenzylidene-4′-oxy)alkanes, have been prepared. In three of the series, the number of methylene groups in the flexible alkyl spacer has been varied from 3 to 12 while the terminal alkyl chain is held constant at either 2, 6 or 10. In the remaining series, the effect of increasing the terminal chain length has been studied by holding the spacer length constant at 3, 4 or 5 methylene units while varying the length of the terminal chain from 0 to 10 carbon atoms. The phase behaviour and transitional properties of these series have been investigated using optical microscopy and differential scanning calorimetry, while the structures of the mesophases have been studied using X-ray diffraction on both powder and aligned samples. This study has revealed novel phase behaviour involving intercalated smectic phases stabilized by the mixed mesogenic group interaction. We have identified the first examples of intercalated smectic C, smectic I, crystal B and crystal J phases and have assigned the layer stacking sequences in the crystal B phases. An extension to the current nomenclature used to describe smectic phases is proposed in order to include these new structural modifications such that, for example, SA_c , refers to the intercalated smectic A phase. The specific interaction between the two unlike groups has a much smaller influence on the nematic-isotropic transition temperatures than it has on the structures of the smectic phases. Quantitative estimates of the nematic-isotropic transition temperatures based on the Marcelja-Luckhurst theory provide further evidence for a specific interaction between the unlike mesogenic groups. Finally, the thermal behaviour of binary mixtures of the analogous symmetric dimers is also found to be governed by the mixed core interaction and intercalated smectic phases are observed in these mixtures.