Is this how bromine spiropyran salt is converted to merocyanine under UV irradiation? A look through the prism of quantum chemical calculations

Abstract

The stability of merocyanine forms formed under UV irradiation of a solution of a spiropyran salt, in which an organic part acts as a cation and a compact bromide ion as an anion, their photophysical properties, and the formation mechanism are studied in this work using time-dependent density functional theory. Theoretical calculations show that TTC and CTT are the most stable open forms (the difference in stability energies is 10.5 and 12.0 kcal mol⁻¹ relative to the formation energy of spiropyran, respectively). The simulated absorption bands in the UV spectrum of the merocyanine forms are observed both in the UV region at 308–366 nm and in the visible region at 544–757 nm due to n → π* and π → π* type transitions. We found that the isomerisation mechanism of spiropyran into merocyanine forms includes two key stages: the ring opening to form cisoid merocyanine forms (except unstable TCC) through conical intersection and their subsequent isomerisation to form stable transoid isomers. The length of the C_spiro–O bond is 1.97 Å and the C1′–C2′–C3′–C4′ angle is 70° in the structure close to conical intersection. The stage that determines the rate of this process is the isomerisation between transoid forms, as in the case of transformation of open merocyanine forms into spiropyran.