The incorporation of thiophene as a core fragment in a mesogen is known to contribute to an increase of optical anisotropy, a decrease of the melting point, a promotion of a negative dielectric anisotropy, a reduction in viscosity, and fast switching times. In this presentation, the synthesis and atomistic-level characterization of novel thermotropic liquid crystals based on thiophene are reported (1-3). In these molecules, a thiophene ring, 1-4 disubstituted phenyl rings, and ester and azomethine linking units form the core fragment, and an alkoxy unit serves as the terminal group. All compounds exhibited an enantiotropic nematic phase, as confirmed by hot-stage polarizing microscope analysis and differential scanning calorimetry. Isotropic 13C chemical shift and 1H-13C dipole-dipole coupling values measured from solid-state NMR experiments on crystalline solid and nematic phases were compared to the values obtained from the static nematic phase. These experiments demonstrate the alignment of molecules in the magnetic field. Lower melting and clearing values are observed when two phenyl rings are part of the mesogen, while the addition of a third phenyl ring increases these values. Two-dimensional PITANSEMA experiments (4) are used to measure the order and geometry of individual chemical groups of these molecules relative to the director of the mesogen accurately. 1. T. Narasimhaswamy, D. K. Lee, N. Somanathan, and A. Ramamoorthy, Chem. Mater., 17, 4567-4569 (2005). 2. T. Narasimhaswamy, D. K. Lee, K. Yamamoto, N. Somanathan, and A. Ramamoorthy, J. Am. Chem. Soc., 127, 6958-6959 (2005). 3. T. Narasimhaswamy, N. Somanathan, D. K. Lee and A. Ramamoorthy, Chem. Mater., 17, 2013-2018 (2005). 4. D. K. Lee, T. Narasimhaswamy, and A. Ramamoorthy, Chem. Phys. Lett., 399, 359-362 (2004).