Impact of mesogenic aromaticity and cyano termination on the alignment and stability of liquid crystal shells.

We carry out a strategic and systematic variation of the molecular structure of liquid crystals (LCs) molded into spherical shells, surrounded by aqueous isotropic phases internally and externally. Contrary to common expectation, based on previous studies that have almost exclusively been carried out with cyanobiphenyl-based LCs, we find that the director field aligns normal to the LC-water interface when we use an LC molecule that is entirely non-aromatic. We propose to explain this by the inability of such an LC to participate in hydrogen bonding, rendering the normal configuration favorable as it minimizes the molecular cross section in contact with the water. We also find that cyano-terminated LC molecules contribute greatly to stabilizing the LC-water interface. This explains why shells made of cyanobiphenyl LCs are much more stable than shells of LCs with non-cyano-terminated molecules, even if the latter exhibit aromatic cores. Unstable LC shells can be stabilized very efficiently, however, through the addition of a low concentration of molecules that are cyano-terminated, preferably below the threshold for dimerization. Our study provides a much clarified understanding of how the molecular structure dictates the stability and alignment of LC shells, and it will enable a diversification of LC shell research and applications to systems where the use of non-cyanobiphenyl LCs is required.