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After the submission of this paper, it came to our attention that similar absorption of the singlet state of benzophenone in water has been observed by Ramseier et al. (J. Phys. Chem. A 2003, 107, 3305).
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The aroyloxyl radicals are known to show absorption in the 600-800 nm range and their reported lifetimes are 0.2-0.5 μs (ref 14). However, we observed no absorption in that range during our experiments, and attempts to observe the aroylbenzoyloxyl radicals were unsuccessful. Ingold and co-workers (ref 14b) had studied a single aroylbenzoyl peroxide and, as was the case with the system we report in this paper, saw no aroylbenzoyloxyl radical absorption. One of the reviewers has pointed out that two-photon absorption could be responsible for extremely fast decarboxylation of the aroylbenzoyloxyl radicals, and we believe this could be the case. The aroyloxyl radicals are known to decarboxylate faster, leading to the formation of the aryl radicals when they absorb at either 308 or 700 nm (ref 14a). It has also been shown that the benzoyloxyl radical that has been stabilized by preparation at low temperatures (67 K) can be photodecar-boxylated with light of 550-1300 nm (Karch, N. J.; Koh, E. T.; Whitsel, B. L.; McBride, J. M. J. Am. Chem. Soc. 1975, 97, 6729).
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1242324786
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Since the triplet states are also quenched by oxygen, the 550 nm absorption might be mistakenly assigned to the triplet state of BPs, as was done by Allen et al. (ref 6), who assigned the 550 nm absorption obtained from the nanosecond LFP of 1 in acetonitrile to its triplet state.
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1242324787
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The only common radical that can be obtained from both 1 and p-iodobenzophenone is the 4-benzoylphenyl radical. The similar ∼560 nm absorption observed previously during nanosecond LFP of 1 was tentatively assigned to the 4-benzoylbenzoyloxyl radical on the basis of the resemblance of its lifetime to that of the benzoyloxyl radical (ref 14). However, the lifetimes of the aroylphenyl radicals have also been found to be in a similar range (∼0.4 μs) and depend on the solvent and concentration of the precursor BPs. The evidence presented in the text clearly suggests that the 550 nm absorption is due to the aroylphenyl radicals.
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We have recently measured the triplet lifetime of p-iodobenzophenone and it was found to be 98.46 ± 2.16 ps in benzene (detailed results will be published elsewhere).
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