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Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative confined in parallelly aligned nanochannels of monolithic, mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3–22 nm) and surface chemistry reveal a competition of radial and axial columnar orders. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau–de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with the channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter.
We report a high-resolution dielectric study on a pyrene-based discotic liquid crystal (DLC) in the bulk state and confined in parallel tubular nanopores of monolithic silica and alumina membranes. The positive dielectric anisotropy of the DLC molecule at low frequencies (in the quasistatic case) allows us to explore the thermotropic collective orientational order. A face-on arrangement of the molecular discs on the pore walls and a corresponding radial arrangement of the molecules is found. In contrast to the bulk, the isotropic-to-columnar transition of the confined DLC is continuous, shifts with decreasing pore diameter to lower temperatures, and exhibits a pronounced hysteresis between cooling and heating. These findings corroborate conclusions from previous neutron and x-ray-scattering experiments as well as optical birefringence measurements. Our study also indicates that the relative simple dielectric technique presented here is a quite efficient method in order to study the thermotropic orientational order of DLC-based nanocomposites.