ABSTRACT
The deuterium NMR spectrum of benzene-d6 in a high field spectrometer (1GHz protons) exhibits a magnetic field-induced deuterium quadrupolar splitting Δν. The magnitude of Δν observed for the central resonance is smaller than that observed for the (13)C satellite doublets Δν'. This difference, Δ(Δν)=Δν'-Δν, is due to unresolved fine structure contributions to the respective resonances. We determine the origins of and simulate this difference, and report pulse sequences that exploit the connectivity of the peaks in the (13)C and (2)H spectra to determine the relative signs of the indirect coupling, JCD, and Δν. The positive sign found for Δν is consonant with the magnetic field biasing of an isolated benzene molecule-the magnetic energy of the aromatic ring is lowest for configurations where the C6 axis is normal to the field. In the neat liquid the magnitude of Δν is decreased by the pair correlations in this prototypical molecular liquid.
ABSTRACT
The unusual exhibition of a biaxial nematic phase in nonlinear thermotropic mesogens derived from the 2,5-oxadiazole biphenol (ODBP) core is placed in a general context; the uniaxial nematic phase of the prototypical rod-like mesogen para-quinquephenyl does not follow the classical mean-field behaviour of nematics, thus questioning the utility of such theories for quantitative predictions about biaxial nematics. The nuclear magnetic resonance spectra of labelled probe molecules dissolved in ODBP biaxial nematic phases suggest that a second critical rotation frequency, related to the differences in the transverse diamagnetic susceptibilities of the biaxial nematic, must be exceeded in order to create an aligned two-dimensional powder sample. Efforts to find higher viscosity and lower temperature biaxial nematics (with lower critical rotation rates) to confirm the above conjecture are described. Several chemical modifications of the ODBP mesogenic core are presented.
ABSTRACT
We have synthesized liquid crystal (LC) mesogens based on a nonlinear oxadiazole unit that exhibit nematic phases near 200 degrees C. Polarized microscopy and conoscopy indicate that these LCs are biaxial nematics. Unambiguous and quantitative evidence for biaxiality is achieved using 2H NMR spectroscopy. "2D powder" spectra, obtained by rotating 2H-labeled samples about an axis perpendicular to the magnetic field at approximately 200 Hz, yield phase biaxiality parameters of approximately 0.1 when coupled with rigorous and proven simulations.
