The photoformation of a phthalide: a ketene intermediate traced by FSRS

Literature Information

Publication Date 2014-11-12
DOI 10.1039/C4CP03351E
Impact Factor 3.676
Authors

Sascha Fröbel, Laura Buschhaus, Torben Villnow, Oliver Weingart, Peter Gilch


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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.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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