Handedness Inversion in Chiral Nematic (Ethyl)cellulose Solutions: Effects of Substituents and Temperature

Various acylates and phenylcarbamates of (ethyl)­cellulose (EC) were synthesized by acylation and carbanilation, respectively, of the residual hydroxyls of an EC (ethyl DS = 2.50). The acyl substituents adopted were propionyl, butyryl, cyclohexanoyl, and adamantoyl groups, and the phenylcarbamoyl substituents included 3-chlorophenylcarbamoyl, 4-chlorophenylcarbamoyl, 3-methylphenylcarbamoyl, and bare phenylcarbamoyl groups. Chiral nematic mesophases of the EC derivatives, formed in chloroform, acetic acid (AA), and dichloroacetic acid (DCA), were examined by various optical techniques for evaluation of the helical pitch (P) in a set of absolute value and twist sense. The lyotropic samples prepared with DCA (20 °C) always assumed a right-handed chiral nematic structure, regardless of the degree of acyl (or phenylcarbamoyl) substitution (DSAcyl (or DSPC), ≤0.50). The chiral nematic series with AA (20 °C) and chloroform (5 °C) showed an inversion of the twist sense from being left-handed to right-handed, when DSAcyl (or DSPC) of each derivative was increased. The critical DS value for the inversion varied depending on the chain length, bulkiness, and polar nature of the employed substituent. For all of the lyotropic series explored, it was generalized that a temperature elevation strengthens a left-handed twisting power in each chiral nematic mesophase. Reversal of the twist handedness was also observed in a cycle of heating and cooling of some chiral nematics in AA. This was interpreted as being due to compensation in the strength of the two chiral interactions, i.e., steric repulsion and dispersion interaction between mesogenic molecules, contributing in mutually opposite signs to the twisting power (2πP –1) of the mesophase.