Femtosecond to microsecond observation of the photochemical reaction of 1,2-di(quinolin-2-yl)disulfide with methyl methacrylate

Abstract

The mechanism of the thiol–ene reaction induced by 330 nm ultraviolet excitation of 1,2-di(quinolin-2-yl)disulfide (QSSQ) in the presence of methyl methacrylate (MMA) is investigated by sub-picosecond to microsecond transient absorption spectroscopy. The measurements, spanning more than seven orders of magnitude of time, directly reveal multiple radical reaction steps. The ground state quinoliene-2-thiyl radical (QS) is formed with a time constant of ∼200 fs by photolysis of QSSQ, followed by (64 ± 1)% decay of the initially formed QS radical because of solvent cage induced geminate recombination and QS dimer formation with a rate coefficient of (3.4 ± 0.2) × 10¹⁰ M⁻¹ s⁻¹ in methanol solution. In MMA solution, the carbon centered radical QS-MMA forms with a bimolecular reaction rate coefficient of (2.8 ± 0.2) × 10⁷ M⁻¹ s⁻¹. The distinct infrared band at 1653 cm⁻¹ assigned to the CO stretch mode of the QS-MMA radical decays rapidly in aerated solution, in contrast to observations in a solution purged of O₂ by N₂ bubbling. This decay is attributed to reaction of the QS-MMA radicals with molecular oxygen, producing peroxy radicals. Kinetic analysis of the intensity of the band at 1653 cm⁻¹ reveals a bimolecular reaction rate coefficient of (3.3 ± 0.3) × 10⁹ M⁻¹ s⁻¹ for the reaction of the QS-MMA radicals with molecular oxygen, and indicates that this reaction step is reversible.