ABSTRACTTo prepare cholesteric liquid crystalline nonlinear optical materials with ability to be vitrified on cooling and form long time stability cholesteric glasses at room temperature, a series of platinum acetylide complexes modified with cholesterol has been synthesized. The materials synthesized have the formula trans-Pt(PR3)(cholesterol (3 or 4)-ethynyl benzoate)(1-ethynyl-4-X-benzene), where R = Et, Bu or Oct and X = H, F, OCH3 and CN. A cholesteric liquid crystal phase was observed in the complexes R = Et, and X = F, OCH3 and CN but not in any of the other complexes. When X = CN, a cholesteric glass was observed at room temperature which remained stable up to 130 °C, then converted to a mixed crystalline/cholesteric phase and completely melted to an isotropic phase at 230 °C. When X = F or OCH3 the complexes were crystalline at room temperature with conversion to the cholesteric phase upon heating to 190 and 230 °C, respectively. In the series X = CN, OCH3 and F, the cholesteric pitch was determined to be 1.7, 3.4 and 9.0 µ, respectively.