Multistep syntheses of new photochromic systems derived from bis-thienylperfluorocyclopentenes are described. They are shown to be thermally stable, fatigue resistant and switch reversibly between colorless open forms and colored closed forms. The incredible stability of these reversible switches led to the attempts of incorporating thermotropic liquid crystalline nature. Polycatenar photochromic esters prepared seem to be mesogenic and thus may form the very first example of liquid crystals with Z-configuration.