Molecular Flexibility and Bend in Semi-Rigid Liquid Crystals: Implications for the Heliconical Nematic Ground State.

The NTB phase phases possess a local helical structure with a pitch length of a few nanometers and is typically exhibited by materials consisting of two rigid mesogenic units linked by a flexible oligomethylene spacer of odd parity, giving a bent shape. We report the synthesis and characterisation of two novel dimeric liquid crystals, and perform a computational study on 10 cyanobiphenyl dimers with varying linking groups, generating a large library of conformers for each compound; this allows us to present molecular bend angles as probability weighted averages of many conformers, rather than use a single conformer. We validate conformer libraries by comparison of interproton distances with those obtained from solution-based 1D 1 H NOESY NMR, finding good agreement between experiment and computational work. Conversely, we find that using any single conformer fails to reproduce experimental interproton distances. We find the use of a single conformer significantly overestimates the molecular bend angle while also ignoring flexibility; in addition, we show that the average bend angle and flexibility are both linked to the relative stability of the NTB phase.