Investigation of solute-solvent interactions of 4′-alkyl-4-cyanobiphenyl liquid crystals using Raman spectroscopy

Liquid crystal materials possess hybrid liquid and solid-like properties with high response to stimuli. The 4′-alkyl-4-cyanobiphenyls (nCB) are an important class of liquid crystals that are widely used for various applications. In this study, six alkylcyanobiphenyl liquid crystal samples (5CB to 10CB) were examined using Raman spectroscopy in a total of twelve solvents of various polarities. The distinctive bands contributed by the LC sample are from C≡N stretch, C–C aromatic ring breathing, C–C biphenyl linking stretch, and C–H in-plane deformation. These modes are found to be responsive to different solvent environments by shifting positions. For instance, the cyano stretching mode of 5CB is blue-shifted from 2229 cm⁻¹ for the pure sample to 2233 cm⁻¹ when measured in hexane due to the repulsive interaction between the mode and the solvent bath. On the other hand, this mode undergoes a red-shift to 2220 cm⁻¹ in methanol due to hydrogen bond interaction between the mode and solvent molecules. Overall, the shift in the position of the vibrational modes of nCB molecules was correlated with solvent properties such as acceptor number, donor number, and Kamlet-Taft dipolarity constants, which are a measure of solvent polarity. In samples with longer alkyl chains (8CB, 9CB, and 10CB), the wavenumber of the stretching modes was generally shifted to around the same position in all the solvents. Such observations are related to the folding back effect and enhanced dimerization constant with an increase in the chain length.