We study the photoresponsive behavior of thin films of supramolecular 4-nitro-4′-hydroxyazobenzenepoly(4-vinylpyridine) complexes. Hydrogen bonding between the phenol and pyridine moieties allows attaching a chromophore to essentially each repeat unit of the polymer, thereby suppressing macroscopic phase separation and crystallization. Moreover, the noncooperative nature of hydrogen bonding leads to random complexation of the chromophores to the polymer backbone, which enables a systematic study of the effect of chromophore concentration on the photo-orientation of the complexes. Two regimes are observed: Photoinduced birefringence increases linearly with the chromophore concentration until nominally every third polymer repeat unit is occupied. Beyond that concentration, a new regime is observed with a drastically steeper slope of increase. The latter regime is connected to the interplay between the formation of a hydrogen-bonded supramolecular complex and intermolecular interactions between the mesogenic chromophores. Such a behavior significantly enhances the birefringence at high concentrations and also leads to high remnant birefringence. Hence, the supramolecular approach yields a superior optical performance compared to guest-host polymers and even surpasses the properties of many covalently functionalized polymers, while still allowing modular tunability of the materials properties.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.