Excited-state proton transfer behavior of 7-hydroxy-4-methylcoumarin in AOT reverse micelles.

The excited-state proton transfer and phototautomerization of 7-hydroxy-4-methylcoumarin (7H4MC) dye has been studied in the confined water pools of AOT reverse micelles using steady-state and time-resolved fluorescence measurements. In the "dry" reverse micelles ([water]/[AOT], w(0) = 0), only the neutral form of the dye is present both in the ground and the excited states. At higher w(0) values, three prototropic forms, namely, neutral, anionic, and tautomeric, can be identified in the excited state, although only the neutral form of the dye is present in the ground state. From steady-state fluorescence results and time-resolved area-normalized emission spectra (TRANES), it is indicated that the anionic and tautomeric forms of the dye are the excited-state reaction products and that they arise apparently independently from the excited neutral form of the dye. In bulk water, however, there is no evidence of the tautomeric species and only the anionic form is observed in the excited state. The fluorescence quenching results of the three forms of 7H4MC by the different quenchers, potassium iodide, aniline, and N, N-dimethylaniline, suggest that the distribution of 7H4MC molecules in the reverse micelles is not diverse but that the different prototropic forms arise from the same population of the excited dye in the interfacial region.