Excited-State Hydroxide Ion Release From a Series of Acridinol Photobases

Yun Xie, Stefan Ilic, Sanja Skaro, Veselin Maslak, Ksenija D. Glusac

The excited-state heterolysis of acridinol-based derivatives leads to the release of the OH- ion and the formation of the corresponding acridinium cations. To evaluate the parameters that control the reaction barriers, the kinetics of excited-state OH- release from a series of acridinol photobases were studied using transient absorption spectroscopy. The rate constants were obtained in three solvents (methanol, butanol and isobutanol), and the data were modeled using Marcus theory. The intrinsic reorganization energies obtained from these fits were found to correlate well with the solvent reorganization energies calculated using dielectric continuum model, suggesting that the excited-state hydroxide ion release occurs along the solvent reaction coordinate. Furthermore, the ability of acridinol photobases to photo-initiate chemical reactions was demonstrated using a Michael addition between dimethylmalonate and nitrostyrene.