Excited-state prototropic equilibrium dynamics of 6-hydroxyquinoline encapsulated in microporous catalytic faujasite zeolites.

Sun-Young Park, Hyunung Yu, Jiho Park, Du-Jeon Jang

Index: Chemistry 16(42) , 12609-15, (2010)

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Abstract

The excited-state proton transfer and geminate recombination of 6-hydroxyquinoline (6HQ) encaged in catalytic Na(+)-exchanged faujasite zeolites X (NaX) and Y (NaY) have been explored by measuring steady-state and picosecond time-resolved spectra. The pathways and rate constants of proton transfer of excited 6HQ are determined by the microscopic environment of zeolitic hosts surrounding the guest molecules. The excited-state proton transfer of a 6HQ molecule encapsulated in a zeolitic nanocavity is initiated by deprotonation of the enolic group to form an anionic intermediate and completed by subsequent protonation of the imino group to form a zwitterionic tautomer. Geminate recombination occurs to compete with proton transfer at each tautomerization step of excited-state 6HQ because of the confined environment of dehydrated zeolitic supercages. Consequently, excited-state equilibria among three prototropic species of 6HQ are established in microporous catalytic faujasite zeolites. Kinetic differences in NaX and NaY are attributed to dissimilarities in acidity/basicity.