Formal intramolecular photoredox reactions of anthraquinones mediated by water

dc.contributor.authorHou, Yunyan
dc.contributor.supervisorWan, Peter
dc.date.accessioned2011-05-26T22:00:03Z
dc.date.available2011-05-26T22:00:03Z
dc.date.copyright2010en_US
dc.date.issued2011-05-26
dc.degree.departmentDept. of Chemistryen_US
dc.degree.levelDoctor of Philosophy Ph.D.en_US
dc.description.abstractThe formal intramolecular photoredox reaction initially discovered for the parent 2- (hydroxymethyl)-9,10-anthraquinone (HMAQ) in aqueous solution was extended to a variety of anthraquinone derivatives 2.1-2.9, biphenyl anthraquinones 3.1-3.4 and acenequinones 4.1-4.4. The purpose of the study was to explore the generality of the unique photochemical reaction involving HMAQ, understand the mechanism of the reaction and develop potential applications. All the anthraquinones studied (except for 2.4) undergo the formal intramolecular photoredox reaction with a range of quantum yields (PHI =0.02-0.7). Mechanistic studies based on the parent compound HMAQ were carried out by product studies, isotope effects, solvent deuterium isotope effects, pH effect, triplet quenching studies, and laser flash photolysis. It was found that the formal intramolecular photoredox reaction involves a highly polarized triplet excited state in which the electron density of the benzylic CH20H moiety is transferred to the central anthraquinone ring. This highly polarized triplet excited state is subsequently trapped adiabatically by protonation at the anthraquinone carbonyl oxygen.en_US
dc.description.scholarlevelGraduateen_US
dc.identifier.urihttp://hdl.handle.net/1828/3319
dc.languageEnglisheng
dc.language.isoenen_US
dc.rights.tempAvailable to the World Wide Weben_US
dc.subjectphotochemistryen_US
dc.titleFormal intramolecular photoredox reactions of anthraquinones mediated by wateren_US
dc.typeThesisen_US

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