Dynamics of electron transfer in amine photooxidation

Journal Article · Wed Aug 13 00:00:00 EDT 1980 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00537a060· OSTI ID:6950945

Peters, K S; Freilich, S C; Schaeffer, C G

Studies were initiated utilizing picosecond (ps) absorption spectroscopy, to directly monitor the dynamics of electron transfer from 1,4-diazabicyclo(2.2.2)octane (Dabco) to the excited states of benzophenone and fluorenone. These two systems were chosen because of their contrasting photochemistry. The quantum yield for photoreduction of benzophenone in polar solvents is generally greater than 0.1, while that of fluorenone is zero. In polar solvents, the proposed mechanism dictates that an electron is transferred to the excited singlet state fluorenone, which then back-transfers the electron, regenerating ground-state fluorenone and amine. Photolysis of benzophenone in the presence of an amine transfers an electron to an excited triplet state, forming an ion pair that is stable relative to diffusional separation. The results of this study verify this proposal.

• Research Organization: Harvard Univ., Cambridge, MA
• OSTI ID: 6950945
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 102:17; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
ALKANES
AROMATICS
AZINES
BENZOPHENONE
CHEMICAL REACTIONS
CYCLOALKANES
DECOMPOSITION
ELECTRON TRANSFER
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
IRRADIATION
KETONES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PULSED IRRADIATION
PYRAZINES
SPECTROSCOPY