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

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• 作者：Yun Xie ; Stefan Ilic ; Sanja Skaro ; Veselin Maslak ; Ksenija D. Glusac
• 刊名：Journal of Physical Chemistry A
• 出版年：2017
• 出版时间：January 19, 2017
• 年：2017
• 卷：121
• 期：2
• 页码：448-457
• 全文大小：550K
• ISSN：1520-5215

文摘

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 OH^– release occurs along the solvent reaction coordinate. Furthermore, the ability of acridinol photobases to photoinitiate chemical reactions was demonstrated using the Michael reaction between dimethylmalonate and nitrostyrene.