Abstract
UV- and IR-induced photoisomerization of acetylacetone trapped in a nitrogen matrix at 4.3 K have been carried out using a tunable optical parametric oscillator type laser, or a mercury vapor lamp, coupled with Fourier Transform IR and UV spectroscopies. After deposition, the main form present in the cryogenic matrix is that chelated (enol). Upon UV irradiation, the intramolecular H bond is broken leading to nonchelated isomers among seven possible open forms. These forms have then been irradiated by resonant pi* <-- pi UV irradiation, or by resonant nuOH irradiation. The selective UV irradiation allows us to suggest a first vibrational assignment while the nuOH irradiation leads us to observe interconversions between the nonchelated isomers. In order to support our vibrational assignment, we have carried out theoretical calculations at the B3LYP/6-311++G(2d,2p) level of theory. This study shows that only five isomers are observed among eight postulated.
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