Time-resolved insight into the photosensitized generation of singlet oxygen in endoperoxides.

ABSTRACT: A synergistic approach combining high-level multiconfigurational static calculations and full-dimensional ab initio surface hopping dynamics has been employed to gain insight into the photochemistry of endoperoxides. Electronic excitation of endoperoxides triggers two competing pathways, cycloreversion and O–O homolysis, that result in the generation of singlet oxygen and oxygen diradical rearrangement products. Our results reveal that cycloreversion or the rupture of the two C–O bonds occurs via an asynchronous mechanism that can lead to the population of a ground-state intermediate showing a single C–O bond. Furthermore, singlet oxygen is directly generated in its most stable excited electronic state 1Δg. The triplet states do not intervene in this mechanism, as opposed to the O–O homoly

SUBMITTER: Martinez-Fernandez L 

PROVIDER: S-EPMC4325559 | biostudies-literature | 2015 Feb

REPOSITORIES: biostudies-literature