DOI | Resolve DOI: https://doi.org/10.1039/c2cp40819h |
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Author | Search for: Brogaard, Rasmus Y.; Search for: Schalk, Oliver1; Search for: Boguslavskiy, Andrey E.1; Search for: Enright, Gary D.2; Search for: Hopf, Henning; Search for: Raev, Vitaly; Search for: Tarcoveanu, Eliza; Search for: Sølling, Theis I.; Search for: Stolow, Albert1 |
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Affiliation | - National Research Council of Canada. Security and Disruptive Technologies
- National Research Council of Canada. Measurement Science and Standards
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Format | Text, Article |
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Abstract | The Paternò–Büchi (PB) reaction between an excited carbonyl compound and an alkene has been widely studied, but so far little is known about the excited-state dynamics of the reaction. In this investigation, we used a compound in which a formyl and a vinyl group are attached to a [2.2]paracyclophane in order to obtain a model system in pre-reactive conformation for the PB reaction. We studied the excited-state dynamics of the isolated molecule in a molecular beam using femtosecond time-resolved photoelectron spectroscopy and ab initio calculations. The results show that inter-system crossing within two picoseconds competes efficiently with the reaction in the singlet manifold. Thus, the PB reaction in this model system takes place in the triplet state on a time scale of nanoseconds. This result stresses the importance of triplet states in the excited-state pathway of the PB reaction involving aromatic carbonyl compounds, even in situations in which the reacting moieties are in immediate vicinity. |
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Publication date | 2012-05-02 |
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In | |
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Language | English |
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Peer reviewed | Yes |
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NPARC number | 21268938 |
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Export citation | Export as RIS |
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Report a correction | Report a correction (opens in a new tab) |
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Record identifier | 74ec4d5a-837d-4b6e-bece-1f8d54c1f049 |
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Record created | 2013-11-27 |
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Record modified | 2020-04-21 |
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