Columnar phases of achiral vanadyl liquid crystalline complexes

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Abstract
Two liquid crystalline vanadyl complexes have been studied by frequency domain dielectric spectroscopy over the range 10 mHz to 13 MHz. The materials exhibit two or three columnar phases denoted Colro, Colrd, and Colhd that were identified by X-ray diffraction. In the higher temperature Colrd phase, a relaxation process in the kHz range is observed that is attributed to the reorientation about the molecular short axis. A pronounced dielectric relaxation process shows up in the low temperature Colro phase at hertz and sub-hertz frequencies. This slow relaxation is assigned to reorientation of the molecular dipoles within the polar linear chains, which are aligned along the column's axis. Triangular wave switching studies at low frequency reveal processes inside the Colro phase which are most probably due to ionic/charges relaxations but a ferroelectric switching for an achiral discotic system cannot be ruled out completely. Below the Colro phase there is an orientationally disordered crystalline Crx phase with disordered side chain dipoles. A dielectric relaxation process connected with the intramolecular relaxation of the alkoxy side chains, similar to the beta-process of polymers, has been found in the lower temperature Crx phase.

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