One Methylene Group in the Side Chain Can Alter by 90 Degrees the Orientation of a Main-Chain Liquid Crystal on a Unidirectional Substrate

The mechanisms of orientation of columnar liquid crystals (LCs) on a PTFE-rubbed surface are explored on a homologous series of symmetrically substituted poly­(di-n-alkylsiloxanes) (PDAS). It is shown that by increasing the side-chain length in steps of one CH₂ group, the orientation of PDAS switches back and forth from perpendicular to parallel with respect to PTFE chains. These changes are sensitive to the smallest possible variation of the macromolecular structure (i.e., modification of the side chain length by just one CH₂ group) reflect the alteration of the alignment mechanism identified as graphoepitaxial or epitaxial for the perpendicular and parallel orientation, respectively. The results show that two orthogonal LC orientations are realizable on the same rubbed substrate, which can open new perspectives in the field of organic and printed electronics such as multidomain LCD technology.