Orientational Order of Difluorinated Liquid Crystals: A Comparative 13C-NMR, Optical, and Dielectric Study in Nematic and Smectic B Phases

Abstract

Structural and orientational order properties of 3Cy2CyBF2 and of 5CyCy2BF2 have been investigated by means of (13)C-NMR, optical, and dielectric spectroscopy methods. In the case of NMR, order parameters have been independently obtained from the analysis of either (13)C-(19)F dipolar couplings or (13)C chemical shift anisotropies, both measured from (13)C-{(1)H} NMR static spectra. The assignment of the (13)C resonances has been carried out thanks to the comparison with solution state spectra and DFT calculations, and the relevant geometrical parameters and (13)C chemical shift tensors needed to derive orientational order parameters have been calculated by DFT methods. In the analysis of (13)C-(19)F dipolar couplings, empirical corrections for vibrations and anisotropic scalar couplings have been included. Dielectric measurements have been performed over a broad frequency range for two orientations of the nematic director with respect to the measuring field. At low frequencies (static case) a positive dielectric anisotropy has been determined, which has enabled the calculation of the order parameters according to a well-tested procedure. At high frequencies the dielectric anisotropy changes its sign, a property which can be useful in designing a dual addressing display. The nematic order parameter determined from optical, dielectric, and NMR methods have been compared: their trends with temperature are very similar, apart from some slight shifts, and were analyzed by Haller and Chirtoc models. The differences among the results obtained by the four methods have been discussed in detail, also with reference to the assumptions and approximations used in each case, and to the results recently reported for similar fluorinated nematogens. The presence of a non-negligible order biaxiality has been related to the presence of a CH2CH2 bridging group, linking one cyclohexylic unit with either the other cyclohexyl or the phenyl ring.