The role of lateral substituent size in azobenzene chromophores on photo- and chiro-optical properties of photoactive polymethacrylates

Three chiral photochromic liquid crystalline polymethacrylates were synthesized and their photo- and chiro-optical properties were studied; the correlations between the properties of the polymers and length of the lateral substituent R were revealed. [Display omitted] •Chiral LC azobenzene-containing polymethacrylates were synthesized.•Azobenzene fragments differ in the size of the lateral substituent (-H, -Me, -Et).•The chiro-, photo-optical properties of the polymers were studied.•Polymers can be considered as promising materials for photonic applications. Properties of functional liquid crystalline (LC) macromolecular materials, especially those showing self-organizing behaviour and targeted for specific purposes, strongly rely on the molecular structure of the mesogens used as side-chains. In order to get inside this relationship, new series of chiral LC polymethacrylates (PMA6Azo-R) with azobenzene groups having different lateral substituents (R), namely the methyl (-Me) and ethyl (-Et) groups on the central benzene ring, were synthesized and their comparative study was carried out. The synthesized polymers consist of photochromic azobenzene fragments that differ in the size of the lateral substituent (R = -H, -Me, -Et). All polymers exhibit the cholesteric phase, whereas the polymer without lateral alkyl group in addition forms the low-temperature SmĈ* phase. Investigations of the photoorientation process under linearly polarised visible light irradiation reveal that an increase in the size of side substituent considerably reduces the values of maximum achievable photoinduced dichroism (from 0.89 for PMA6Azo-H to 0.33 for PMA6Azo-Et that is associated with a decrease in the degree of mesogen anisometry). The effect of the lateral substituent size in azobenzene photochrome on the chiro-optical properties and mesomorphic behaviour of studied polymers was established. The presence of the lateral substituent in the photochrome/mesogen fragment leads to a significant decrease in isotropization temperature. Chiro-optical properties of the polymers and their photoswitching were studied, and it was found, that the introduction of the lateral substituent in the azobenzene fragment prevents the formation of exciton couples, that leads to a decrease in the circular dichroism (CD) values. UV irradiation and E-Z isomerisation of the azobenzene chromophores results in complete disappearance of CD signal; subsequent visible light irradiation does not lead to its fu