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Solvent viscosity influence on the chemiexcitation efficiency of inter and intramolecular chemiluminescence systems

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Abstract

The effects of the medium viscosity on the chemiexcitation quantum yields of the induced decomposition of 1,2-dioxetanes (highly efficient intramolecular CIEEL system) and the catalyzed decomposition of diphenoyl peroxide and a 1,2-dioxetanone derivative (model systems for the intermolecular CIEEL mechanism, despite their low efficiency) are compared in this work. Quantum yields of the rubrene catalyzed decomposition of diphenoyl peroxide and spiro-adamantyl-1,2-dioxetanone as well as the fluoride induced decomposition of a phenoxy-substituted 1,2-dioxetane derivative are shown to depend on the composition of the binary solvent mixture toluene/diphenyl ether, which possess similar polarity parameters but different viscosities. Correlations of the quantum yield data with the medium viscosity using the diffusional and the frictional (free-volume) models indicate that the induced 1,2-dioxetane decomposition indeed occurs by an entirely intramolecular process and the low efficiency of the intermolecular chemiluminescence systems (catalyzed decomposition of diphenoyl peroxide and 1,2-dioxetanone derivative) is not primarily due to the cage escape of radical ion species.

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Authors and Affiliations

  1. Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo, Brazil

    Muhammad Khalid, Sergio P. Souza Jr. & Wilhelm J. Baader

  2. Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, SP, Brazil

    Luiz F. M. L. Ciscato & Fernando H. Bartoloni

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  1. Muhammad Khalid
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  2. Sergio P. Souza Jr.
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  3. Luiz F. M. L. Ciscato
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  5. Wilhelm J. Baader
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Correspondence to Wilhelm J. Baader.

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Khalid, M., Souza, S.P., Ciscato, L.F.M.L. et al. Solvent viscosity influence on the chemiexcitation efficiency of inter and intramolecular chemiluminescence systems. Photochem Photobiol Sci 14, 1296–1305 (2015). https://doi.org/10.1039/c5pp00152h

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