To furnish new insight into structure−property relationships governing glassy nematic liquid crystals, novel material systems were synthesized and characterized. Highly ordered, solid films were also prepared via spin-coating for the determination of optical birefringence. It was found that a linear nematogen, such as the cyanoterphenyl group, contributes to an elevated glass transition temperature and a wide nematic fluid temperature range with a mixed or an extended core structure. However, an angular nematogen, such as the cyanophenylnaphthyl group, is more versatile in inducing glass formation with a broader range of core structures. Morphologically stable, glassy nematics with a Tg close to 130 °C, a Tc close to 350 °C, a nematic fluid temperature range of 265 °C, and an optical birefringence of 0.44 accomplished in this study represent significant improvements over existing materials. A stereochemical modification of the bicyclooctene ring from an exo-, exo- to an endo-, and exo-configuration, fluor...