title: Chemiexcitation Efficiency of Intermolecular Electron-transfer Catalyzed Peroxide Decomposition Shows Low Sensitivity to Solvent-cavity Effects.
abstract: Intermolecular chemically initiated electron exchange luminescence (CIEEL) systems are known to possess low chemiluminescence efficiency; whereas, the corresponding intramolecular transformations are highly efficient. As the reasons for this discrepancy are not known, we report in this work our studies of the solvent-cavity effect on the efficiency of two intermolecular CIEEL systems, the catalyzed decomposition of diphenoyl peroxide and of a relatively stable 1,2-dioxetanone derivative, spiro-adamantyl-1,2-dioxetanone. The results indicate a very low medium viscosity effect on the quantum yields of these systems, a priori not compatible with these bimolecular transformations, showing also that their low efficiency cannot be due to solvent-cavity escape of intermediate radical ion pairs. In addition, the solvent-cage effect on the CIEEL efficiency, after the occurrence of the initial electron transfer, proved also to be very low, indicating the intrinsic low viscosity effect on the chemiexcitation step. Therefore, it is concluded that the low efficiency of these systems is intrinsic to the chemiexcitation step and cannot be improved by medium viscosity effects, being possibly due to sterical hindrance on charge-transfer complex formation in the initial step of the CIEEL.
authors.affiliation: Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo, Brazil.
authors.forename: Muhammad
authors.initials: M
authors.lastname: Khalid
authors.affiliation: Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo, Brazil.
authors.forename: Sergio P
authors.initials: SP
authors.lastname: de Souza
authors.affiliation: Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, Brazil.
authors.forename: Fernando H
authors.initials: FH
authors.lastname: Bartoloni
authors.affiliation: Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo, Brazil.
authors.forename: Felipe A
authors.initials: FA
authors.lastname: Augusto
authors.affiliation: Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo, Brazil.
authors.forename: Wilhelm J
authors.initials: WJ
authors.lastname: Baader