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

Augusto, Felipe A.Uppsala universitet,Teoretisk kemi,Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Av Prof Lineu Prestes 748, Sao Paulo, Brazil. (författare)

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

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.

Francés-Monerris, AntonioUppsala universitet,Teoretisk kemi,Univ Valencia, Inst Ciencia Mol, POB 22085, Valencia 46071, Spain. (författare)
Fdez. Galván, Ignacio,1977-Uppsala universitet,Teoretisk kemi(Swepub:uu)ignga749 (författare)
Roca-Sanjuán, DanielUniv Valencia, Inst Ciencia Mol, POB 22085, Valencia 46071, Spain. (författare)
Bastos, Erick L.Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Av Prof Lineu Prestes 748, Sao Paulo, Brazil. (författare)
Baader, Wilhelm J.Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Av Prof Lineu Prestes 748, Sao Paulo, Brazil. (författare)
Lindh, Roland,1958-Uppsala universitet,Teoretisk kemi(Swepub:uu)rolli621 (författare)
Uppsala universitetTeoretisk kemi (creator_code:org_t)

Ingår i:Physical Chemistry, Chemical Physics - PCCP: Royal Society of Chemistry19:5, s. 3955-39621463-90761463-9084

Av författaren/redakt...: Augusto, Felipe ...; Francés-Monerris ...; Fdez. Galván, Ig ...; Roca-Sanjuán, Da ...; Bastos, Erick L.; Baader, Wilhelm ...; visa fler...; Lindh, Roland, 1 ...; visa färre...

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