Can even-membered liquid crystal dimers exhibit the twist-bend nematic phase? The preparation and properties of disulphide and thioether linked dimers

Cyanobiphenyl-based liquid crystal dimers containing a disulfide link in the spacer, the 4-[4-[2-[2-[4-(4-cyanophenyl)phenyl]alkyldisulfanyl]alkyl]-phenyl]benzonitriles (CBnSSnCB), are reported. The alkyl fragment is varied from two to nine carbon atoms, and all eight homologues exhibit nematic behaviour. In addition, the dimer containing heptamethylene fragments (CB7SS7CB) exhibits a twist-bend nematic phase despite having an even-membered spacer. The values of the nematic–isotropic transition temperature, T_NI, are higher for dimers containing an odd number of carbon atoms in each alkyl fragment. This surprising behaviour is interpreted in terms of the C-S-S-C torsion angle being around 88° that ensures that the molecular shape is bent irrespective of the parity of the alkyl fragments. For odd-membered fragments, however, the average shape is less bent and higher values of T_NI are observed. The more uniform molecular curvature of CB7SS7CB accounts for the observation of the N_TB phase. We also report the behaviour of two members of the 4-[4-[3-[2-[4-(4-cyanophenyl)phenyl]alkyldisulfanyl]-alkyl]phenyl]benzonitriles (CBnSmCB) which contain a thioether link embedded in the spacer. Both dimers exhibited nematic behaviour. The thioether link reduces the value of T_NI compared to that of the dimer with an alkyl spacer. A much larger decrease in the nematic-twist-bend nematic temperature is observed and is attributed to a change in shape.