Photoionization of Indole in Alkaline Aqueous Solutions at 77°K

Abstract

The photoionization process of indole in alkaline aqueous solutions at 77°K and the recombination process of trapped electron with its mother molecule were investigated. The fluorescence spectrum of indole in these glassy media depended on the NaOH concentration; the disappearance of the 325 nm band at the NaOH concentrations higher than 5 M with the appearance of a fluorescence band at 375 nm. The latter emission is possibly ascribed to the fluorescence of indole anion formed by proton dissociation in the excited singlet state of indole. The intensities of the 375 nm band and the ESR signal due to trapped electrons were dependent on the NaOH concentration and increased steeply with increasing the NaOH concentration. There was a parallel relation between the indole anion concentration and the trapped electron density to some extent. The dependence of the ESR signal intensity on irradiation intensity suggested that the photoionization of indole in alkaline aqueous solution occurred through a two photon process. The presence of a photoactive intermediate for absorbing the second photon was further investigated with simultaneous irradiation of two different wavelength lights. The trapped electron was detrapped with the irradiation of visible light (e.g. 580 nm), and its recombination with mother molecule caused an emission with the same spectrum as indole phosphorescence. The molecular species of the photoactive intermediate in alkaline aqueous solutions seems to be the indole anion. The photoionization in NaOH aqueous solution at 77°K was also compared with that in methanolic glassy solution.