The 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. / Graduate
| Identifer | oai:union.ndltd.org:uvic.ca/oai:dspace.library.uvic.ca:1828/3319 |
| Date | 26 May 2011 |
| Creators | Hou, Yunyan |
| Contributors | Wan, Peter |
| Source Sets | University of Victoria |
| Language | English, English |
| Detected Language | English |
| Type | Thesis |
| Rights | Available to the World Wide Web |
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