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Issue 10, 2012
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Photochemistry of acetylacetone isolated in parahydrogen matrices upon 266 nm irradiation

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Abstract

The photochemistry of the chelated enol form of acetylacetone (AcAc) was investigated by UV excitation of the S2 state at 266 nm in parahydrogen matrices, complemented by experiments in neon and normal hydrogen matrices. Infrared (IR) spectroscopy, combined with theoretical calculations, was used to identify the photoproducts. Isomerization towards various non-chelated forms (no intramolecular H-bond) of AcAc is the dominant channel whereas fragmentation is very minor. The isomerization kinetics is monitored by IR spectroscopy. Among the seven non-chelated conformers of AcAc, only three are formed in parahydrogen matrices, whereas four are observed in normal hydrogen matrices. This difference suggests that an active tunnelling process between conformers occurs in parahydrogen but is quenched in normal hydrogen where guest–host interactions are stronger. Fragmentation and isomerization of excited AcAc are discussed in the light of these new data. The role of the intermediate triplet state in the S2 → S0 relaxation is confirmed, as the importance of phonons in the condensed phase.

Graphical abstract: Photochemistry of acetylacetone isolated in parahydrogen matrices upon 266 nm irradiation

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Publication details

The article was received on 07 Dec 2011, accepted on 16 Jan 2012 and first published on 16 Jan 2012


Article type: Paper
DOI: 10.1039/C2CP23913B
Citation: Phys. Chem. Chem. Phys., 2012,14, 3450-3459
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    Photochemistry of acetylacetone isolated in parahydrogen matrices upon 266 nm irradiation

    R. R. Lozada-García, J. Ceponkus, M. Chevalier, W. Chin, J. Mestdagh and C. Crépin, Phys. Chem. Chem. Phys., 2012, 14, 3450
    DOI: 10.1039/C2CP23913B

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