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- W2013212440 abstract "The photo-isomerization of o-acetylbenzaldehyde (oABA) in acetonitrile was studied by femto- and nanosecond transient absorption spectroscopy. Spectroscopic signatures are assigned with the aid of TD-DFT, TD-CAM-DFT and DFT-MRCI computations. The isomerization yields a lactone, 3-methylphthalide (3MP), with a quantum yield of 0.3 (30%). As evidenced by femtosecond stimulated Raman spectroscopy (FSRS), the isomerization proceeds via a ketene intermediate. It is formed within ∼2-3 ps after photo-excitation. Intersystem crossing (ISC) populating the triplet state of oABA seems to compete with the ketene formation. Experiments on the non-reactive meta- and para-derivatives, which undergo efficient ISC with time constants of 5 ps, support this statement. The triplet state of oABA also contributes to the ketene formation, presumably involving a biradical intermediate. The ketene exhibits a lifetime of 1.4 μs and generates an additional intermediate in the cascade towards the lactone." @default.
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- W2013212440 date "2015-01-01" @default.
- W2013212440 modified "2023-09-27" @default.
- W2013212440 title "The photoformation of a phthalide: a ketene intermediate traced by FSRS" @default.
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- W2013212440 doi "https://doi.org/10.1039/c4cp03351e" @default.
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