The influence of the imine bond direction on the phase behaviour of symmetric and non-symmetric liquid crystal dimers

The synthesis and characterisation of two series of liquid crystal dimers are reported: the symmetric 1,5-bis(4 '- oxyanilinebenzylidene-4-alkane)pentanes (m-O5O-m), and the non-symmetric 1-(4-cyanobiphenyl-4 '-yloxy)-5-(4 '-oxyanilinebenzylidene-4-alkane)pentanes (CBO5O-m). In the acronyms for each series m refers to the terminal chain length. The m-O5O-m series showed monotropic nematic phases for m = 1-7. Smectic behaviour emerged at m = 7 and nematic behaviour extinguished at m = 8. For the CBO5O-m series, an enantiotropic nematic phase is seen for m = 1-10. In addition, m = 1 shows a twist-bend nematic phase, and m = 9 and 10 an interdigitated smectic A phase. These series are compared to the corresponding dimers in which the imine link in the benzy-lideneaniline fragments is reversed, the m.O5O.m and CBO5O.m series. For the symmetric dimers, reversing the imine link has a small effect on the nematic-isotropic transition temperatures, TNI, but a much larger effect on the smectic-isotropic transition temperatures, TSmI. In both cases, the m.OnO.m series shows the higher values. The values of TNI are also slightly higher for the CBO5O.m series than the CBO5O-m series. Surprisingly, the values of TSmI are higher for the CBO5O-m than for the CBO5O.m series. These differences are discussed in terms of the changes in shape and electronic distributions arising from reversing the imine link.