Thermal, optical and photoinduced properties of a series of homo and co-polyimides with two kinds of covalently bonded azo-dyes and their supramolecular counterparts

• Photosensitive and processable (co)polyimides with azo-chromophores were synthesized.
• Azopolymers contained one or two different chromophores in the polymer repeating unit.
• The supramolecular counterparts of polymers with covalently bonded dyes were also prepared.
• The physical and the light-induced properties of obtained polymers were investigated.

The paper describes the synthesis and characterization of new aromatic polyimides with one or two different moieties of the azo-dyes covalently attached to the polymer backbone and their supramolecular analogues. Azo-functionalized polyimides were prepared using post-polymerization method including the introduction of Disperse Red 13 and/or 4-[4-(6-hydroxyhexyloxy)phenylazo]pyridine to homo and co-polyimides containing hydroxyl groups via Mitsunobu reaction. The degree of functionalization of polymers with chromophores was estimated by UV–Vis spectroscopy. Polyimides containing hydroxyl groups were applied as matrixes to create supramolecular systems based on hydrogen bonds. Hydrogen-bond interactions in azosystems were studied by FTIR spectroscopy. The polymers were characterized by 1H NMR, FTIR, X-ray, UV–Vis, DSC and TGA methods. The photoisomerization process was investigated in supramolecular systems. The light-induced anisotropy was studied in a holographic gratings recording experiment and by photoinduced birefringence measurements. The polymer films were investigated by atomic force microscopy (AFM) after the diffraction grating recording to confirm formation of surface relief gratings (SRGs). To the best of our knowledge, that the first time photoinduced anisotropy has been studied by birefringence measurements in polyimides containing two different azo-dyes.

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