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Authordc.contributor.authorRobinson-Duggon, José 
Authordc.contributor.authorMariño-Ocampo, Nory 
Authordc.contributor.authorBarrias, Pablo 
Authordc.contributor.authorZúñiga-Núñez, Daniel 
Authordc.contributor.authorGünther, Germán 
Authordc.contributor.authorEdwards, Ana María 
Authordc.contributor.authorGreer, Alexander 
Authordc.contributor.authorFuentealba, Denis 
Cita de ítemdc.identifier.citationJournal of Physical Chemistry A, Volumen 123, Issue 23, 2019, Pages 4863-4872
Abstractdc.description.abstractExperiments and theoretical calculations by density functional theory (DFT) have been carried out to examine a self-sensitized type I photooxidation of toluidine blue O (TBO+). This study attempts to build a connection between visible-light photolysis and demethylation processes of methylamine compounds, such as TBO+. We show that controlled photoinduced mono- and double-demethylation of TBO+ can be achieved. The kinetics for the appearance rate of the mono-demethylated TBO+ and the double-demethylated TBO+ were found to fit pseudo-first-order kinetics. DFT calculations have been used to examine the demethylation of TBO+ and included N,N-dimethylaniline as a model compound for TBO+. The results show an oxygen-dependent demethylation process. The mechanism for the sequential methyl loss is proposed to be due to H• or e-/H+ transfer to 3TBO+∗ followed by a reaction of TBO+• with O2, yielding a C-peroxyTBO+• intermediate. Instead of aminyl radical peroxyl formation, i.e., N-peroxyTBO+•, the C-centered peroxyTBO+• is favored, that upon dimerization (Russell mechanism) leads to dissociation of formaldehyde from the methylamine site.
Publisherdc.publisherAmerican Chemical Society
Type of licensedc.rightsAttribution-NonCommercial-NoDerivs 3.0 Chile
Link to Licensedc.rights.uri
Sourcedc.sourceJournal of Physical Chemistry A
Keywordsdc.subjectPhysical and Theoretical Chemistry
Títulodc.titleMechanism of Visible-Light Photooxidative Demethylation of Toluidine Blue O
Document typedc.typeArtículo de revista
Indexationuchile.indexArtículo de publicación SCOPUS

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Except where otherwise noted, this item's license is described as Attribution-NonCommercial-NoDerivs 3.0 Chile