Time‐Resolved Fluorescence and Transient Spectroscopy in Determining Photochemical and Photophysical Channels in Reacting Systems in Solutions and Microheterogeneous Media

Abstract

Abstract— Characterization of short‐lived intermediates in homogeneous and microheterogeneous systems has been carried out using time‐resolved spectroscopic techniques. The data obtained from these techniques have been analyzed in a relatively unconventional manner to elucidate complex transient behavior for two reactive systems. The highly nonexponential fluorescence decay for a series of fraws‐stilbene‐derivatized amphiphiles that readily form bilayer systems in aqueous media has been analyzed using a distribution of lifetimes analysis (DLA). The utility of DLA for quantitative studies was first determined by simulation of artificial decay data. Despite some limitations in DLA, qualitative conclusions as to the nature of the fluorescing species may be drawn when supplementary information such as steady‐state spectroscopic data are also considered. The results indicate that the observed fluorescence originates from different types of excited‐state species that consist of two or more trans‐stilbene units; one of the emissions is attributed to the excited state of a ground‐state aggregate while the other is assigned to an excimer that may arise from a 'defect'in the bilayer. The nonexponential nature of the decays is attributed to distributions of environments experienced by the fluorescing species. Electron transfer (ET) reactions between several excited pinacols and carbon tetrachloride in solution have been found to yield products with quantum yields that are higher than unity in the presence of oxygen, suggesting a chain mechanism for product formation. In these systems both the donor and the acceptor undergo bond fragmentation following the initial ET step. The individual steps involved in the proposed mechanism for these systems have been investigated in part using different steady‐state and time‐resolved laser spectroscopic techniques. However, it was also necessary to utilize pulse radiolysis in order to confirm the involvement of certain radical intermediates that were not observable by the usual flash photolysis techniques.