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Journal of Chemistry
Volume 2017 (2017), Article ID 1903981, 8 pages
https://doi.org/10.1155/2017/1903981
Research Article

Theoretical Analysis of the Effect Provoked by Bromine-Addition on the Thermolysis and Chemiexcitation of a Model Dioxetanone

1Chemistry Research Unit (CIQUP), Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal
2LACOMEPHI, Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal
3Chemistry Research Unit (CIQUP), Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal

Correspondence should be addressed to Luís Pinto da Silva

Received 9 February 2017; Accepted 12 April 2017; Published 26 April 2017

Academic Editor: Teik-Cheng Lim

Copyright © 2017 Luís Pinto da Silva et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

Chemi-/bioluminescence are phenomena in which chemical energy is converted into electronically excited singlet states, which decay with light emission. Given this feature, along with high quantum yields and other beneficial characteristics, these systems have gained numerous applications in bioanalysis, in biomedicine, and in the pharmaceutical field. Singlet chemiexcitation is made possible by the formation of cyclic peroxides (as dioxetanones) as thermolysis provides a route for a ground state reaction to produce singlet excited states. However, such thermolysis can also lead to the formation of triplet states. While triplet states are not desired in the typical applications of chemi-/bioluminescence, the efficient production of such states can open the door for the use of these systems as sensitizers in photocatalysis and triplet-triplet annihilation, among other fields. Thus, the goal of this study is to assess the effect of heavy atom addition on the thermolysis and triplet chemiexcitation of a model dioxetanone. Monobromination does not affect the thermolysis reaction but can improve the efficiency of intersystem crossing, depending on the position of monobromination. Addition of bromine atoms to the triplet state reaction product has little effect on its properties, except on its electron affinity, in which monobromination can increase between 3.1 and 8.8 kcal mol−1.