Seven members of the homologous series of the liquid crystal dimers, the bis(ω-(cholesteryloxycarbonyl)alkyl)disulfides, which contain a sulfur−sulfur link in the flexible spacer have been synthesised and their liquid crystal properties characterised. The dimers are referred to using the acronym Chol-n-SS-n-Chol in which n denotes the number of carbon atoms linking the cholesteryl-based groups and the sulfur atoms, and was varied between 3, 5, 6, 8, 10, 11 and 12. All seven homologues exhibit a chiral nematic phase and for the longest three members a smectic A phase was also observed. An odd−even effect is apparent in both the transition temperatures and the values of the entropy change associated with the chiral nematic−isotropic transition, ΔSN*I /R, in which dimers with even values of n show the higher values. This is interpreted in terms of the average molecular shapes in which the C−S−S−C dihedral angle is around 90°. The values of ΔSN*I/R shown by these dimers are very small for liquid crystal dimer...

Cholesteryl-based liquid crystal dimers containing a sulfur–sulfur link in the flexible spacer

The first series of liquid crystal dimers to contain an isoflavone-based moiety has been prepared, the α-(4'-methoxy-3-phenyl-4H-1-benzopyran-4-one-7-oxy)-ω-(4-methoxyazobenzene-4'-oxy)alkanes. All eight members of this homologous series exhibit an enantiotropic nematic phase. The nematic–isotropic transition temperatures and associated entropy changes exhibit a dramatic dependence on the length and parity of the flexible spacer. This characteristic behaviour for a homologous series of liquid crystal dimers has been interpreted in terms of how the flexible alkyl spacer controls the average molecular shape. A comparison of the transitional properties of this series with those of the symmetric parent dimers, the α,ω-bis(4-methoxyazobenzene-4'-oxy)alkanes, reveals that replacing a methoxyazobenzene unit by the isoflavone-based group reduces the melting point but increases the nematic–isotropic transition temperature. Three other non-symmetric dimers are reported: 1-(4'-methoxy-3-phenyl-4H-1-benzopyran-4-one-...

Non-symmetric liquid crystal dimers containing an isoflavone moiety

Liquid crystals with 1,3,4-oxadiazole units in the aromatic core have attracted considerable attention due to their rich mesophases, high photoluminescence quantum yields, good electron transporting ability and excellent thermal stabilities. In this feature article, 1,3,4-oxadiazole-based liquid crystals are classified into three categories according to their different molecular shapes and molecular weight: calamitic and discotic monomers, symmetric and non-symmetric dimers, and polymers including main-chain, side-chain and mesogen-jacketed types. The structure–property relationships of this kind of liquid crystal are discussed in-depth, with an emphasis on strategies to devise columnar and biaxial nematic mesophases with a low temperature range.

1,3,4-Oxadiazole based liquid crystals

A new class of blue light emitting liquid crystalline star-shaped molecules based on 1,3,4-thiadiazoles have been designed and synthesized. These compounds were investigated using polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction, cyclic voltammetry and photophysical studies. In comparison to their 1,3,4-oxadiazole counterparts, these thiadiazole-based molecules are promising as they stabilize the hexagonal columnar phases over a broad thermal range. The thermal behavior and photophysical properties of these new star-shaped molecules are extremely dependent on the number and types of peripheral tails in the molecular structure. 1,3,4-Thiadiazole derivatives exhibit sky-blue emission in solution, unlike the deep blue emission of 1,3,4-oxadiazole derivatives. They also exhibit a lower band gap as compared to their oxadiazole counterparts and offer great potential in organic light emitting diode applications.

Columnar self-assembly of star-shaped luminescent oxadiazole and thiadiazole derivatives

The synthesis and characterisation of two new series of liquid crystal tetramers in which four mesogenic groups are linked via three alkyl spacers is reported. In each series the length of the outer two spacers, n, is varied between 3, 4, 5, 7, 10 and 11 methylene units while the central spacer length, m, is either 5 or 6 methylene units. The outer two mesogenic groups are cholesteryl-based, Chol, while the inner two are Schiff's bases, SB. The tetramers are referred to by the acronym Chol-n-SB-m-SB-n-Chol. All twelve tetramers exhibit an enantiotropic chiral nematic phase. The chiral nematic-isotropic transition temperatures and associated entropy changes depend critically on the combination of spacers in the tetramer and this is interpreted in terms of average molecular shapes. The tetramers with m = 5 and n = 5, 7, and m = 6 and n = 3, 4, 5, 7, show a monolayer chiral smectic C* phase, the driving force for which may be the mismatch in the cross-sectional areas of the differing mesogenic groups. The tetramers with m=6 and n = 10, 11 show a quadruply intercalated smectic A phase characterised by a smectic periodicity to estimated molecular length ratio of just 0.23. The driving force for the formation of this phase is thought to be specific electrostatic interactions between the unlike mesogenic units while the formation of the phase is strongly dependent on the length and parity of the spacers due to packing constraints. On cooling, a new phase transition is seen, possibly driven by conformational changes in the outer flexible spacers, for both these tetramers from the intercalated smectic A phase to an intercalated alternating chiral smectic C* phase in which the layers consist of either the mixed mesogenic groups or solely the cholesteryl-based moieties.

Chiral liquid crystal tetramers

A series of non-symmetric liquid crystal compounds consisting of two different semi-rigid anisometric cores, namely 1,3,4-oxidiazole and biphenyl units, and two short terminal groups, have been synthesised in good yield. It has been shown by polarising optical microscopy and differential scanning calorimetry that all these compounds display liquid crystalline behaviour, with nematic and/or smectic A mesophases. The nature of the mesophases is dependent on the electronic properties of the terminal groups. In methylene chloride solution all the compounds displayed a room temperature emission with λmax at 358–396 nm and quantum yields of 0.29–0.56. The effect of the terminal groups on the mesomorphic and photoluminescent properties is briefly discussed in the context of their electronic characteristics.

Miao Zhang

Papers

Non-symmetric liquid crystal dimers based on 1,3,4-oxadiazole derivatives: synthesis, photoluminescence and liquid crystal behaviour