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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
Effect of Alkyl- vs Alkoxy-Arene Substituents on the Deactivation Processes and Fluorescence Quantum Yields of
Joseph P Dinnocenzo1, Olesya Haze1, Cavan Fleming1
1Department of Chemistry, University of Rochester, Rochester, New York 14627-0216, United States.
Abstract:
Decay processes of exciplexes of cyanoanthracenes with alkylbenzene donors were compared to those with alkoxybenzenes. For the three decay processes of exciplexes, the radiative rate constant (kf) of alkoxy derivatives is slightly lower than those of alkylbenzenes at the same average exciplex energy. However, the corresponding deactivation rate constants, intersystem crossing (kisc) and nonradiative decay (knr), are considerably higher. Consequently, the fluorescence quantum yields of the alkoxybenzene exciplexes are one-half to one-fifth of the corresponding alkylbenzenes at comparable emission energies. This trend is solvent-independent. The results can be rationalized in terms of the differing electronic character of the donor radical cation moieties in the alkoxy- vs alkylbenzene exciplexes and differences in their reorganization energies. The impact of these results for the design of exciplexes that emit more efficiently is discussed.
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