Azobenzene-Based Main-Chain Liquid Crystalline Polymers Bearing Periodically Installed Alkyl, PEG, or Fluoroalkyl Segments and Photoisomerization Studies

In the present study, liquid crystalline polymers (LCPs) were prepared by melt-transesterification of azobenzene-bearing diols and diethyl malonate (DEM) derivatized monomers. The effect of the nature and length of the installed pendant segments on the mesomorphic properties of the prepared LCPs was investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), and polarized optical microscopy (POM) studies. The formation of layered morphology was inferred from X-ray scattering analysis arising from the colocation of rigid azobenzene moieties in one layer and the flexible pendant segments in alternate layers due to the zigzag folding of the polymer backbone. The linear variation of the interlamellar spacing with the number of carbon atoms in the pendant alkyl segments corroborates the proposed zigzag backbone folding in the polymers. The rate constant values obtained from the photoisomerization studies of the isomeric polymers and model compound, which are in the same ballpark, reveal that the photoisomerization process of such polymers is not affected by the position or size of the azobenzene unit. © 2024 Taylor & Francis Group, LLC.