A combined theoretical and experimental study on the mechanism of spiro-adamantyl-1,2-dioxetanone decomposition

Abstract

1,2-Dioxetanones have been considered as model compounds for bioluminescence processes. The unimolecular decomposition of these prototypes leads mainly to the formation of triplet excited states whereas in the catalysed decomposition of these peroxides singlet states are formed preferentially. Notwithstanding, these cyclic peroxides are important models to understand the general principles of chemiexcitation as they can be synthesised, purified and characterised. We report here results of experimental and theoretical approaches to investigating the decomposition mechanism of spiro-adamantyl-1,2-dioxetanone. The activation parameters in the unimolecular decomposition of this derivative have been determined by isothermal kinetic measurements (30–70 °C) and the chemiluminescence activation energy calculated from the correlation of emission intensities. The activation energy for peroxide decomposition proved to be considerably lower than the chemiluminescence activation energy indicating the existence of different reaction pathways for ground and excited state formation. These experimental results are compared with the calculations at the complete active space second-order perturbation theory (CASPT2), which reveal a two-step biradical mechanism starting by weak peroxide bond breakage followed by carbon–carbon elongation. The theoretical findings also indicate different transition state energies on the excited and ground state surfaces during the C–C bond cleavage in agreement with the experimental activation parameters.