Molecular structure and the twist-bend nematic phase: the role of spacer length in liquid crystal dimers

Abstract

The liquid crystal dimers, the 1-(4-substitutedazobenzene-4′-yloxy)-4-(4-cyanobiphenyl-4′-yl)butanes (CB4OABX), are reported in which the terminal substituent is either a methyl, methoxy, butyl, butyloxy, cyano or nitro group. The butyloxy spacer endows these dimers with the required molecular curvature to exhibit the twist-bend nematic phase in addition to showing the conventional nematic phase. Their transitional properties are compared to those of the corresponding dimers with either a pentyloxy or hexyloxy spacer. As expected, the even-membered pentyloxy-based dimers show the highest nematic–isotropic transition temperature, TNI, and exhibit smectic behaviour. These observations are attributed to their linear molecular shapes. The values of both the twist-bend nematic–nematic transition temperature, TNTBN, and TNI increase on passing from the butyloxy to hexyloxy spacer, but the change in TNI is greater than that in TNTBN. Thus, the ratio TNTBN is greater for the shorter spacer reinforcing the view that molecular curvature drives the formation of the NTB phase relative to the N phase. By comparison, the melting point decreases on passing from the butyloxy to hexyloxy spacer. Thus, increasing molecular curvature simultaneously increases both the melting point and NTB phase stability and this highlights the design challenge in obtaining dimers that exhibit enantiotropic NTB–I transitions.