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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Mechanism of activated chemiluminescence of cyclic peroxides: 1,2-dioxetanes and 1,2-dioxetanones

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Author(s):
Augusto, Felipe A. ; Frances-Monerris, Antonio ; Galvan, Ignacio Fdez ; Roca-Sanjuan, Daniel ; Bastos, Erick L. ; Baader, Wilhelm J. ; Lindh, Roland
Total Authors: 7
Document type: Journal article
Source: Physical Chemistry Chemical Physics; v. 19, n. 5, p. 3955-3962, FEB 7 2017.
Web of Science Citations: 12
Abstract

Almost all chemiluminescent and bioluminescent reactions involve cyclic peroxides. The structure of the peroxide and reaction conditions determine the quantum efficiency of light emission. Oxidizable fluorophores, the so-called activators, react with 1,2-dioxetanones promoting the former to their first singlet excited state. This transformation is inefficient and does not occur with 1,2-dioxetanes; however, they have been used as models for the efficient firefly bioluminescence. In this work, we use the SA-CASSCF/CASPT2 method to investigate the activated chemiexcitation of the parent 1,2-dioxetane and 1,2-dioxetanone. Our findings suggest that ground state decomposition of the peroxide competes efficiently with the chemiexcitation pathway, in agreement with the available experimental data. The formation of non-emissive triplet excited species is proposed to explain the low emission efficiency of the activated decomposition of 1,2-dioxetanone. Chemiexcitation is rationalized considering a peroxide/activator supermolecule undergoing an electron-transfer reaction followed by internal conversion. (AU)

FAPESP's process: 14/22136-4 - Use of green solvents and their mixtures for optimizing chemical processes
Grantee:Omar Abou El Seoud
Support type: Research Projects - Thematic Grants
FAPESP's process: 14/14866-2 - Intermolecular interactions involving betalains
Grantee:Erick Leite Bastos
Support type: Regular Research Grants