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Photophysical and Photochemical Processes in Zeolite Cavities: the Effects of Ion-Exchanged Alkali Metal Cations On the Excited States of Xanthone and the Photolysis of 2-Pentanone

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The characteristic properties of xanthone phosphorescence and of 2-pentanone photolysis in alkali metal cation-exchanged zeolites have been investigated to clarify the effect of the micro-environment of host-adsorbents on the photophysical and photochemical properties of guest-molecules in restricted void spaces. The enhancement of the phosphorescence yields of xanthone included in zeolites is observed by changing the exchangeablealkali metal cation from Li+ to Cs+. Simultaneously, the phosphorescence lifetimes were observed to continuously shorten by changing the cation from Li+ to Cs+. These results suggest that the external heavy-atom effect deriving from the alkali metal cations on the singlet-triplet transitions of xanthone molecules stabilized on alkali metal cations in the order of Li+, Na+, K+, Rb+, and Cs+. The yields for the photolysis of 2-pentanone included in zeolites increase with changing the alkali metal cation from Li+ to Cs+. IR investigations of the adsorption state of 2-pentanone indicate that the strength of the interaction between the alkali metal cations and 2-pentanones decreases by changing the cation from Li+ to Cs+, which results in a longer lifetime of 2-pentanone. The selectivity of propylene formation is dramatically increased by changing the cation from Li+ to Cs+. The enhanced formation of propylene is associated with the hydrogen absorption from propyl radicals by lattice oxygen, their basicity increasing by changing the cation from Li+ to Cs+. Thus, these changes in the zeolite cavities modified by exchanging cations caused significant effects not only on the excited state but also on the following chemical reactions of ketones.

Affiliations: 1: Department of Applied Chemistry, College of Engineering, University of Osaka Prefecture, Gakuen-cho I-I, Sakai, Osaka 593, Japan


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