Optical and computational study of the trans ↔ cis reversible isomerization of the commercial bis-azo dye Bismarck Brown Y.

The trans - cis - trans isomerization behaviour of Bismarck Brown Y (BBY) during and after irradiation with visible light, was characterized in detail for the first time by means of optical pump-probe experiments, to study the geometric inter-conversion of bis-azobenzene both in solution and embedded in multi-layered polymeric thin films. The rate constants observed for the thermal cis - trans back isomerization permit a determination of how the thermal isomerization is influenced by its local environment. In both solution and when incorporated into multi-layered thin films, the thermal relaxation observed for the commercial azo dye BBY showed a highly unusual biexponential decay, which clearly demonstrates two distinct isomerization processes. The cis decay showed an anomalous fast isomerization process on the timescale of milliseconds, followed by a slower isomerization process with a cis lifetime on the order of seconds. It was further observed that the faster isomerization process was influenced more by its local environment than was the slower process. The faster isomerization process also displayed a higher rate constant in aprotic solvents such as THF and DMF compared to that observed in protic solvents such as ethanol and water. Additionally, a higher rate constant was observed in solution compared to the multi-layered thin films where motion of the azo molecules was likely more restricted. Following recrystallization of the BBY azo dye, the more expected monoexponential decay was observed for the cis isomer in solution, with a single cis lifetime calculated on the timescale of seconds. This timescale corresponded well to values predicted by density functional theory calculations.