Efficiency of intermolecular chemiluminescence systems lacks significant solvent cavity effect in binary toluene/diphenylmethane mixtures

Autor(es)

Khalid, Muhammad ^[1] ; Oliveira, Marcelo A. ^[1] ; Souza, Jr., Sergio P. ^[1] ; Ciscato, Luiz F. M. L. ^[2] ; Bartoloni, Fernando H. ^[2] ; Baader, Wilhelm J. ^[1]

Afiliação do(s) autor(es)

^[1] Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, BR-05508000 Sao Paulo, SP - Brazil

^[2] Univ Fed ABC, Ctr Ciencias Nat & Humanas, Santo Andre - Brazil

• Tipo de documento: Artigo Científico
• Fonte: JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY; v. 312, p. 81-87, NOV 1 2015.
• Citações Web of Science: 8

Resumo

Chemiluminescence transformations have found widespread analytical and bioanalytical application, however, a general principle which governs the efficiency of chemiluminescence transformations, specifically the catalyzed and unimolecular decomposition of cyclic peroxides, is still not known. Thus, the solvent viscosity influence on the singlet quantum yield in catalyzed diphenoyl peroxide and spiro-adamantyl-1,2-dioxetanone decomposition is studied in the present work. Both reactions do not show significant quantum yield increase within the viscosity range studied (0.56-2.57 cP) using binary toluene/diphenylmethane mixtures. However, the induced decomposition of a phenoxy-substituted 1,2-dioxetane derivative in identical conditions showed to be more sensitive to solvent viscosity effects. These results indicate, for the first time, that the classical intermolecular electron transfer initiated chemiluminescence systems, catalyzed decomposition of diphenoyl peroxide and 1,2-dioxetanones, are not subject to significant solvent cavity effects. Therefore, their low quantum efficiencies cannot be due to solvent cavity escape of intermediate radical ion species during the chemiexcitation process. Additionally, it can be concluded that the highly efficient induced decomposition of phenoxy-substituted 1,2-dioxetanes should occur mainly by an entirely intramolecular process. (C) 2015 Elsevier B.V. All rights reserved. (AU)

• Processo FAPESP: 05/58320-4 - Efeito da estrutura e do meio de reação sobre a quimiluminescência de dioxetanonas
• Beneficiário: Fernando Heering Bartoloni
• Modalidade de apoio: Bolsas no Brasil - Doutorado Direto
• Processo FAPESP: 12/02428-5 - Peróxidos orgânicos cíclicos: síntese e mecanismo de redução
• Beneficiário: Luiz Francisco Monteiro Leite Ciscato
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 14/22136-4 - Uso de solventes verdes e suas misturas na otimização de processos químicos
• Beneficiário: Omar Abou El Seoud
• Modalidade de apoio: Auxílio à Pesquisa - Temático