Time-resolved ultraviolet-vis

Time-resolved spectroscopic techniques are important and effective tools for mechanistic photochemical studies. The most widely used of these tools, time-resolved ultraviolet-visible (UV-Vis) absorption spectroscopy, has been applied to a variety of problems since its introduction by Norrish and Porter [1] over 50 years ago. Although a great deal of information about the reactivity of organic photochemical intermediates (e.g., excited states, radicals, carbenes, and nitrenes) in solution at ambient temperatures has been amassed with this technique, only limited structural information can be extracted from such investigations because absorption bands are usually quite broad and featureless. Questions of bonding, charge distribution, and solvation (in addition to those of dynamics) are more readily addressed with time-resolved vibrational spectroscopy. 

As stated earlier, polymer deposition occurs by precipitation of the oligomers when their chain length attains a value of critical solubility [38]. The growth of PT and poly(bithiophene) has been studied by time-resolved ultraviolet visible (UV-vis) spectroscopy. Comparison of the spectra of the reaction solution with those of authentic neutral thiophene oligomers has led to the conclusion that oligomers formed by 7-12 monomer units are formed in solution during electropolymeriza-... 

In principle, absorption spectroscopy techniques can be used to characterize radicals. The key issues are the sensitivity of the method, the concentrations of radicals that are produced, and the molar absorptivities of the radicals. High-energy electron beams in pulse radiolysis and ultraviolet-visible (UV-vis) light from lasers can produce relatively high radical concentrations in the 1-10 x 10 M range, and UV-vis spectroscopy is possible with sensitive photomultipliers. A compilation of absorption spectra for radicals contains many examples. Infrared (IR) spectroscopy can be used for select cases, such as carbonyl-containing radicals, but it is less useful than UV-vis spectroscopy. Time-resolved absorption spectroscopy is used for direct kinetic smdies. Dynamic ESR spectroscopy also can be employed for kinetic studies, and this was the most important kinetic method available for reactions... 

Time-resolved spectroscopy (stopped-flow ultraviolet-visible (UV-vis) spectroscopy at -90° C, proprionitrile or acetonitrile, [O2] S> [complex]) has been used to characterize intermediates and evaluate the mechanism of the peroxo complex formation (see Fig. 16) (196). Based on the similarity of the spectral features with known superoxo copper(lI) and peroxo-dicop-per(ll) complexes (262, 268, 281) the mechanism shown in Scheme 17 was proposed, and the spectra of the superoxo copper(II) and peroxo-dicop-per(II) complexes were determined (see Table XI). For steric reasons and in... 

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