title: Optical and electron paramagnetic resonance studies of the excited states of 4-tert-butyl-4'-methoxydibenzoylmethane and 4-tert-butyl-4'-methoxydibenzoylpropane.
abstract: The excited states of 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM) and 4-tert-butyl-4'-methoxydibenzoylpropane (BM-DBP), the model of the keto form of BM-DBM, have been studied through measurements of UV absorption, fluorescence, phosphorescence, and electron paramagnetic resonance spectra in ethanol at 77 K. The energy levels and lifetimes of the lowest excited triplet (T(1)) states of BM-DBP, dibenzoylpropane (DBP), the model of the keto form of dibenzoylmethane (DBM), and the keto and enol forms of BM-DBM and DBM were determined. The energy level of the T(1) state of the keto form is much higher than that of the enol form in BM-DBM. The effect of tautomerization on the T(1) lifetime is small in DBM but large in BM-DBM. The methoxy and tert-butyl groups play an important role in lengthening the T(1) lifetimes of BM-DBP and the keto form of BM-DBM. The nature of the T(1) states of the keto and enol forms of BM-DBM can be explained in terms of the mixing of the (3)npi* and (3)pipi* states. The observed energy levels and the lifetimes of the T(1) states of the UV absorbers provide a useful suggestion for designing more photostable UV absorbers.
authors.affiliation: Department of Chemistry, Graduate School of Engineering, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan. akikuchi@ynu.ac.jp
authors.forename: Azusa
authors.initials: A
authors.lastname: Kikuchi
authors.forename: Nozomi
authors.initials: N
authors.lastname: Oguchi
authors.forename: Mikio
authors.initials: M
authors.lastname: Yagi