AUTHOR=Kim Mikhail , Hillel Coral , Edwards Kayrel , Borchers Tristan H. , Mermut Ozzy , Pietro William J. , Barrett Christopher J. TITLE=Azo dye polyelectrolyte multilayer films reversibly re-soluble with visible light JOURNAL=Frontiers in Materials VOLUME=11 YEAR=2024 URL=https://www.frontiersin.org/journals/materials/articles/10.3389/fmats.2024.1334863 DOI=10.3389/fmats.2024.1334863 ISSN=2296-8016 ABSTRACT=

Polymeric multilayer films were prepared using a layer-by-layer (LBL) technique on glass surfaces, by repeated and sequential dipping into dilute aqueous solutions of various combinations of water-soluble polyanions (polyacrylic acid (PAA)), polycations (polyallylamine hydrochloride (PAH) or chitosan (CS)), with bi-functional water-soluble cationic azo dyes bismark brown R bismarck brown red or bismark brown Y (BBY), or anionic azo dyes allura red (ALR) or amaranth (AMA), as ionic cross-linkers. The electrostatically-assembled ionically-paired films showed good long-term stability to dissolution, with no re-solubility in water. However, upon exposure to low power visible light under running water, the films photo-disassembled back to their water-soluble constituent components, via structural photo-isomerization of the azo ionic crosslinkers. The relative rate of the disassembly (RRD) of the films was established using UV-Vis spectroscopy, demonstrating that these assemblies can in principle represent fully recyclable, environmentally structurally degradable materials triggered by exposure to sunlight, with full recovery of starting components. A density functional theory treatment of the allura red azo dye rationalizes the geometrical isomerization mechanism of the photo-disassembly and provides insight into the energetics of the optically-induced structural changes that trigger the disassembly and recovery.