Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

<p>The synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CB<i>n</i>CB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CB<i>n</i>OCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBO<i>n</i>OCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBO<i>n</i>OCB dimer and lowest for the CB<i>n</i>CB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (<i>T</i><sub>N<sub>TB</sub><sub>N</sub></sub>) is higher for the CB<i>n</i>OCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBO<i>n</i>OCB dimers, a virtual value of <i>T</i><sub>N<sub>TB</sub><sub>N</sub></sub> was estimated for CBO3OCB and <i>T</i><sub>N<sub>TB</sub><sub>N</sub></sub> was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CB<i>n</i>CB or CB<i>n</i>OCB series. The dependence of <i>T</i><sub>N<sub>TB</sub><sub>N</sub></sub> on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape.</p>