Acid Yellow 9 Azo Dye Gets the Blues: An Optical Spectroscopy and DFT Study of Unusual Photochemistry in Multilayer Films with PAH and Chitosan

Multilayer and free-standing films self-assembled from water-soluble anionic azo dye acid yellow 9 (AY9) and both poly(allylamine hydrochloride) (PAH), and chitosan (CS) cationic polyelectrolytes were fabricated from water solution using a layer-by-layer (LbL) technique and characterized by UV-Vis and Raman spectroscopy. Observations were made of a strong, unexpected, and highly unusual colour change from deep red to a distinct dark blue upon exposure of the multilayer films to an acidic environment. The colour change was attributed to the multilayer films only and was not observed either for the polymer or the dye alone, or their mixture in water solution, nor when cast as free-standing films. The significant blue shift of the absorption peaks was quantified with UV-Vis spectroscopy, and a proposed explanation is presented based on Density Functional Theory (DFT) calculations exploring possible and most likely acid-base equilibria configurations of the azo dye that result from being self-assembled.