Picosecond studies on the photodissociation dynamics of aromatic endoperoxides

Abstract

Studies on various aromatic endoperoxides (POs) reveal a different photodynamic behavior despite similar excitation conditions and despite similar chromophore structures. Using picosecond laser pump-probe technique it was found that heterocoerdianthrone (HECD), dissolved in dichloromethane, is produced from photocycloreversion of its endoperoxide with a time constant of τ=40±10 ps. Since the lifetime of the photoreactive S3 state is less than 3 ps, a two-step mechanism is expected. Photocleavage of the endoperoxide of anthradichromene (ADCPO) happens in 55±15 ps, whereas the endoperoxides of dimethylhomöocoerdianthrone (HOCDPO) and dimethoxyhomöocoerdianthrone (DMHDPO) photodissociate much faster. For their photodissociation we can state an upper time limit of 5 ps. The results of polarization and solvent dependent experiments demonstrate that the observed rise of signal is directly correlated with the formation of the parent compound in the ground state. The dynamics of the photodissociation of HECPO does not depend on polarity or viscosity of solvent. Therefore, an oxciplex configuration or an intermediate zwitterion cannot be involved in the photocycloreversion of aromatic endoperoxides. The model of a biradical mechanism must be claimed instead.