Structure studies of the nematic phase formed by bent-core molecules

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.

A biaxial nematic phase had been predicted with D(2h) symmetry, wherein the mesogen's long and short transverse axes are simultaneously aligned along the two orthogonal, primary and secondary directors, n and m, respectively. The unique low-angle x-ray diffraction patterns in the nematic phases exhibited by three rigid bent-core mesogens clearly reveal their biaxiality. The results of x-ray diffraction can be readily reproduced by ab initio calculations that explicitly include the bent-core shape in the form factor and assume short-range positional correlations.