Chiral Phases of a Confined Cholesteric Liquid Crystal: Anchoring-Dependent Helical and Smectic Self-Assembly in Nanochannels

Chiral liquid crystals (ChLCs) allow a fundamental insight into the interplay of molecular chirality and the formation of macroscopic, self-assembled helices. They also exhibit unique optical properties, in particular huge polarization rotation, which is employed in a wide range of photonic technologies. Here, we present a study of linear and circular optical birefringence in combination with X-ray diffraction experiments on an archetypical ChLC, i.e., the cholesteric ester CE6, confined in cylinders of mesoporous alumina and silica with distinct polymer surface graftings resulting in normal or tangential wall anchoring. The unconfined ChLC exhibits a discontinuous, first-order isotropic-to-chiral nematic (cholesteric) phase transition with the formation of double-twist helices and a discontinuous cholesteric-to-smectic A transition. The thermotropic behavior of the confined ChLC, explored in a channel radii range of 7-21 nm, deviates substantially from bulk behavior. There is no isotropic state. In contrast, a chiral paranematic phase with a preferred arrangement of the ChLC at the channel wall is found. For normal anchoring, a radial-escape structure evolves upon cooling. The phase transition to the smectic phase is completely suppressed. For tangential anchoring, a large optical activity indicates a continuous paranematic-to-cholesteric transition with double-twist helices aligned parallel to the long axes of the cylinders. Upon cooling, these helical structures, known as basic building blocks of blue ChLC phases, transform in a continuous manner to a cylinder-aligned smectic A phase.

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Chiral Phases of a Confined Cholesteric Liquid Crystal: Anchoring-Dependent Helical and Smectic Self-Assembly in Nanochannels