Enhanced photoinduced mass migration in supramolecular azopolymers by H-bond driven positional constraint. Issue 34 (6th August 2021)

• Record Type: Journal Article
• Authors: Borbone, Fabio; Oscurato, Stefano Luigi; Del Sorbo, Salvatore; Pota, Filippo; Salvatore, Marcella; Reda, Francesco; Maddalena, Pasqualino; Centore, Roberto; Ambrosio, Antonio
• Is Part Of: Journal of materials chemistry. Volume 9:Issue 34(2021)
• Page Start: 11368
• Page End: 11375
• Publication Date: 2021-08-06
• Subjects: Materials -- Periodicals; Chemistry, Analytic -- Periodicals; Optical materials -- Research -- Periodicals; Electronics -- Materials -- Research -- Periodicals; 543.0284
• DOI: 10.1039/d1tc02266k
• Languages: English
• ISSNs: 2050-7526

Abstract

Abstract : SRG inscription on azopolymers films is strongly enhanced by constrained azobenzene–chain interaction established through double H-bond supramolecular synthon. Selective removal of azobenzene from patterned samples is possible by solvent rinse. Abstract : Here we investigated the role of hydrogen bonding in the design of supramolecular azopolymers with a highly directional and constrained azobenzene–chain interaction involving the aromatic ring of the photoactive molecule, by exploiting the 2-aminopyrimidine/carboxylic acid supramolecular synthon as the tool for molecular recognition. We have shown that this approach is advantageous for producing affordable and versatile photopatternable azomaterials by complexation with polyacrylic acid (PAA). Molecular model complexes were successfully prepared and characterized by X-ray diffraction analysis and FTIR spectroscopy to reveal the multiple, non-ionic interaction occurring between the azobenzene units and the polymer chains. Surface photopatterning of thin films, driven by the typical mass migration phenomenon occurring in azopolymers, resulted strongly enhanced with increasing azobenzene content until equimolar composition. Results show that polymers with synthon-based azobenzenes markedly outperform single H-bonded systems bearing azomolecules with similar structure and electronic properties. We finally demonstrated that the azobenzene units can be easily extracted from a photopatterned film by a simple solvent rinse and without any chemical pre-treatment, leaving the periodicity of the inscribed surface relief gratings unaltered. This result was enabled by the orthogonal solubility of the components in the supramolecular system.