Issue 10, 2012
From the journal:

Physical Chemistry Chemical Physics

Photochemistry of acetylacetone isolated in parahydrogen matrices upon 266 nm irradiation†

Rolando R. Lozada-García,ab   Justinas Ceponkus,*ac   Michèle Chevalier,a   Wutharath Chin,a   Jean-Michel Mestdaghd  and  Claudine Crépin*a  

* Corresponding authors

a Institut des Sciences Moléculaires d'Orsay, UMR 8214, Univ. Paris-Sud, CNRS, Orsay, France
E-mail: claudine.crepin-gilbert@u-psud.fr, justinas.ceponkus@ff.vu.lt

b Departamento de Matemática y Computacíon, Instituto Superior de Tecnologías y Ciencias Aplicadas, La Habana, Cuba

c Dept. of General Physics and Spectroscopy, Vilnius University, Vilnius, Lithuania

d CNRS, IRAMIS, SPAM, Laboratoire Francis Perrin, URA 2453, F-91191 Gif-sur-Yvette, France

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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Article information

DOI
https://doi.org/10.1039/C2CP23913B
Article type
Paper
Submitted
07 Dec 2011
Accepted
16 Jan 2012
First published
16 Jan 2012

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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