Substituent effects on the triplet-triplet absorption spectra of coumarin and its derivatives |
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Authors: | Bryan R. Henry Edward A. Lawler |
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Affiliation: | Department of Chemistry, University of Maniloba, Winnipeg, Canada R3T 2N2 |
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Abstract: | Preliminary work on the triplet-triplet (T-T) absorption of coumarin and two of its 4-hydroxy substituted derivatives is extended to four additional substituted coumarins in order to investigate substituent effects on T-T absorption in these molecules. A steady cross Illumination technique is used in EPA glass at 77° K. Measurements of the decay of T-T absorption are carried out with a flash technique and a comparison made with phosphorescence lifetimes to verify the triplet nature of the absorption. The observed T-T spectra show a marked dependence on the presence and position of hydroxy substitution. An explanation is developed based on the mixing of character into the lowest triplet state. The effect of methyl substitution is also investigated and, although it leads to relatively small changes in the T-T spectra, the results suggest that it plays a role in the susceptibility of the molecules to photochemical change. |
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