New 6,6′-disubstituted-binaphthol derivatives as chiral dopants: Synthesis and temperature dependence of molecular conformations

Abstract

A number of new chiral binaphthol (BN) derivatives with different substituents R,R′ in the 6,6′-positions in open (BN-diethylethers) and bridged forms (BN-acetals) have been synthesized. The syntheses of the chiral 6,6′-disubstituted-2,2′-diethoxy-1,1′-binaphthyls (R,R′ = -CH'CHCHO, -CH'CH-(p-BrPh), -CH'CH-(p-CHOPh)) and the chiral 9,14-disubstituted-dinaphtho [2,1-d:1′,2′-f][1,3] dioxepins with R,R′ = -CH'CH-(p-BrPh), -CH'CH-(p-CHOPh) are reported for the first time. The possible liquid crystalline properties and molar twisting powers (β_M) in three different nematic liquid crystals (LCs) of the BN derivatives were investigated. Derivatives with spatially extended substituents in the 6,6′-positions (e.g. styryl or vinyl) show unusually high molar twisting power (up to 124.5μm⁻¹). A direct correlation between the magnitude of β_M and the length of the substituents was found. Bridged forms, in which the dihedral angle θ between the naphthyl moieties is ≊ 54°, show higher twisting power than the corresponding open forms, where θ is allowed to vary around 90° resulting in an equilibrium between transoid and cisoid forms. From the different temperature dependencies of β_M of the open and bridged BN_s, a molecular model was developed relating the molecular conformation and twisting power. Although no mesophase was found in any of the compounds synthesized, they can be considered as important precursors for the synthesis of potential chiral BN-containing LCs.