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Issue 24, 2012
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The Paternò–Büchi reaction: importance of triplet states in the excited-state reaction pathway

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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.

Graphical abstract: The Paternò–Büchi reaction: importance of triplet states in the excited-state reaction pathway

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Publication details

The article was received on 12 Nov 2011, accepted on 02 May 2012 and first published on 02 May 2012


Article type: Paper
DOI: 10.1039/C2CP40819H
Citation: Phys. Chem. Chem. Phys., 2012,14, 8572-8580
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    The Paternò–Büchi reaction: importance of triplet states in the excited-state reaction pathway

    R. Y. Brogaard, O. Schalk, A. E. Boguslavskiy, G. D. Enright, H. Hopf, V. Raev, E. Tarcoveanu, T. I. Sølling and A. Stolow, Phys. Chem. Chem. Phys., 2012, 14, 8572
    DOI: 10.1039/C2CP40819H

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