Abstract
Electron transfer (ET) reactions play a key role in both natural (photosynthesis, metabolism) and industrial processes (photography, polymerization, solar cells). The study of intermolecular photo-induced ET reactions in solution is complicated by diffusion. In fact, as soon as the latter is slower than the ET process, it is not anymore possible to directly measure kET, the intrinsic ET rate constant. One way to circumvent this problem is to work in a reacting solvent. However, in this case, the relationship between the observed quenching rate constant and kET is not clear. Indeed, it has been suggested that several solvent molecules could act as efficient donors. In this situation, the measured rate constant is the sum of the individual kET. This chapter presents investigation of the influence of solute-solvent interactions on the quenching dynamics of perylene (Pe) and derivatives in an electron donating solvent, N,N-dimethylaniline (DMA). The fluorescence quenching of Pe and derivatives is investigated by fluorescence up conversion. Excitation is performed with the frequency-doubled output of a Ti:Sapphire amplifier. The instrument response time is around 240 fs with 0.4 mm thick samples. The data are analyzed by iterative re-convolution of the instrument response function with trial functions. For most samples, measurements are carried out at three different wavelengths.
Published Version
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