Revisiting photoisomerization in fluorinated analogues of acetylacetone trapped in cryogenic matrices
Résumé
UV-induced processes are commonly studied in acetylacetone analogues. In this contribution, we revisit the existing work on the photoisomerization process in some of the fluorinated analogues of acetylacetone, i.e., trifluoroacetylacetone (F3-acac) and hexafluoroacetylacetone (F6-acac). We performed selective UV laser excitation of these molecules trapped in soft cryogenic matrices, namely neon and parahydrogen, and probed by vibrational spectroscopy. Clear spectroscopy of 3 isomers of F6-acac and 6 isomers of F3-acac is obtained, including the first characterization of a second open enol isomer of hexafluoroacetylacetone. In addition, we present the electronic absorption spectra of both molecules in cryogenic matrices before and after specific UV irradiations, giving new data on the electronic transitions of photoproducts. Vibrational and electronic experimental results are analyzed and discussed within comparisons with DFT and TD-DFT calculations. Our findings contribute to a deeper understanding of the photoisomerization process in these molecules after electronic excitation in gas and condensed phase.
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AcAcF6_AcAcF3_iso.pdf (1.69 Mo)
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AcAcF6_AcAcF3_SI.pdf (3.67 Mo)
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