Phase Behaviors and Photoresponsive Thin Films of Syndiotactic Side‐Chain Liquid Crystalline Polymers with High Densely Substituted Azobenzene Mesogens

Azobenzene‐containing polymers (azopolymers) are a kind of fascinating stimuli‐responsive materials with broad and versatile applications. In this work, a series of syndiotactic C1 type azopolymers of Pm‐Azo‐Cn with side‐chain azobenzene mesogens of varied length alkoxy tails (n=1, 4, 8, 10) and different length alkyl spacers (m=6, 10) have been prepared via Rh‐catalyzed carbene polymerization. The thermal properties and ordered assembly structures of thus synthesized side chain liquid crystalline polymers (SCLCPs) have been systematically investigated with differential scanning calorimetry (DSC), polarized optical microscopy (POM) and variable‐temperature small/wide‐angle X‐ray scattering (SAXS/WAXS) analyses. P10‐Azo‐C1 and P10‐Azo‐C4 with shorter alkoxy tails exhibited hierarchical structures SmB/Colob and transformed into SmA/Colob at a higher temperature, while P10‐Azo‐C8 and P10‐Azo‐C10 with longer alkoxy tails only displayed side group dominated layered SmB phase and transformed into SmA phase at higher temperatures. For P6‐Azo‐C4 with a shorter spacer only showed a less ordered SmA phase owing to interference by partly coupling between the side chain azobenzene mesogens and the helical backbone. More importantly, the series high densely substituted syndiotactic C1 azopolymer thin films, exhibited evidently and smoothly reversible photoresponsive properties, which demonstrated promising photoresponsive device applications.