Biphasic tautomerization dynamics of excited 7-hydroxyquinoline in reverse micelles

Abstract

The excited-state tautomerization dynamics of 7-hydroxyquinoline in the water pools of reverse micelles has been investigated by monitoring time-resolved fluorescence spectra and kinetics as well as static absorption and emission spectra with a variation of water content and isotopic fractionation. The normal and the tautomeric species are found to reside preferentially in the bound- and the free-water regions of the micelles, respectively. The excited-state tautomerization of the normal species in the bound-water layers is suggested to occur via two different channels, depending on rotamers at the moment of excitation. The cis tautomerizes via proton relay from the enol group to the imino group along a hydrogen-bonded water bridge, unusual in water but common in alcohols, whereas the trans tautomerizes via the stepwise individual acid-base reactions of two prototropic groups as found in bulk water. Proton relay can take place because water in the pools has substantially reduced polarity and disrupted hydrogen-bond networks compared with bulk water.