Abstract
The Norrish Type I and Type II reactions in the photolysis of 2-pentanone included within the alkali metal cation-exchanged ZSM-5 zeolite have been investigated by experimental and theoretical approaches. Changes in the molecular environment of the zeolite cavities by exchanging the cations had significant effects not only on the adsorption state but also on the photochemical reactions of the ketones included within the zeolite cavities. The yields of the photolysis decreased and the ratio of the Type I/Type II reactions increased, respectively, by changing the ion-exchanged cations from Cs+ to Li+. The observed IR and phosphorescence spectra of the adsorbed ketones and the ab initio molecular orbital calculations of this host-guest system indicate that the ketones interact with two different adsorption sites, i.e. the surface OH groups and alkali metal cations, while the interaction between the ketones and cations increased by changing the cations from Cs+ to Li+. Molecular orbital calculations were also carried out and indicated that the zeolite framework promotes the delocalization of the charge density of the alkali metal cations which can modify the interaction between the adsorbed ketones and cations, resulting in significant changes in the photolysis of these ketones.
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Yamashita, H., Nishimura, M., Bessho, H. et al. Effect of ion-exchanged alkali metal cations on the photolysis of 2-pentanone included within ZSM-5 zeolite cavities: a study of ab initio molecular orbital calculations. Research on Chemical Intermediates 27, 89–102 (2001). https://doi.org/10.1163/156856701745159
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DOI: https://doi.org/10.1163/156856701745159