Chemiluminescence Efficiency of Catalyzed 1,2-Dioxetanone Decomposition Determined by Steric Effects

• Published in: Journal of organic chemistry 2015-04, Vol.80 (8), p.3745-3751
• Main Authors: Bartoloni, Fernando Heering, de Oliveira, Marcelo Almeida, Ciscato, Luiz Francisco Monteiro Leite, Augusto, Felipe Alberto, Bastos, Erick Leite, Baader, Wilhelm Josef
• Format: Article
• Language: English
• Subjects: Catalysis; Heterocyclic Compounds, 1-Ring - chemistry; Luminescence; Luminescent Measurements; Organic Chemistry Phenomena; Peroxides - chemistry
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.5b00515

The chemiluminescent decomposition of 1,2-dioxetanones (α-peroxylactones), catalyzed by an appropriate fluorescent activator, is an important simple model for efficient bioluminescent transformations. In this work, we report experimental data on the catalyzed decomposition of two spiro-substituted 1,2-dioxetanone derivatives, which support the occurrence of an intermolecular electron transfer from the activator to the peroxide. The low efficiency of the studied systems is associated with steric hindrance during the chemiexcitation sequence, rationalized using the concept of supermolecule formation between the peroxide and the catalyst. This approach explains the difference in the chemiexcitation efficiencies in the decomposition of four-membered cyclic peroxide derivatives: 1,2-dioxetanes, 1,2-dioxetanones, and 1,2-dioxetanedione (the intermediate in the peroxyoxalate reaction), which are the most important model compounds for excited-state formation in chemiluminescence and bioluminescence processes.