Radical pair optical absorption detection

Two papers have been presented on the photochemistry of 5-methylphena-zinium salts in aqueous solution. Fluorescence, optical flash photolysis, and electron paramagnetic resonance (e.p.r.) techniques have been used to elucidate various aspects of product formation and quantum yield. Two products have been identified, namely the 5-methyl-10-hydrophenazinium cation radical (MPH ) and the pyocyanine (l-hydroxy-5-methyl-phenozinium) cation (PyH ) in a stoicheiometric ratio of 2 1. The quantum yield of formation of (MPH ) was found to be 0.29 0.03 at pH 7.0 and 1.1 0.1 at pH 3.0. The triplet state of MP (Ti) has also been detected by triplet-triplet absorption and is found to have a lifetime of 0.5 ns. Flash photolysis and e.p.r. have also been used to study a geminate triplet radical pair obtained from hydrogen abstraction by excited triplet acetone from propan-2-ol. The authors demonstrate that the geminate pairs contribute most of the polarization in photochemically-induced dynamic electron polarization (CIDEP) as compared with free random-phase pairs. 

One of the topics to which Radiation Chemistry has made many significant and highly visible contributions is that of free radical chemistry . An interesting group within organic radicals is that where the spin is located on a heteroatom. Such radicals often exhibit quite different properties as compared to C-centered radicals owing to the influence of lone electron pairs on their overall electronic structure. Research on these transients flourished particularly since the advent of time-resolved techniques such as pulse radiolysis and flash photolysis which allowed their direct detection on real time. Because of their electronic structure hetero-centered radicals most often exhibit intense and thus easily detectable optical absorptions in the UV, visible and near-IR. 

Radical anions are produced in a number of ways from suitable reducing agents. Common methods of generation of radical anions using LFP involve photoinduced electron transfer (PET) by irradiation of donor-acceptor charge transfer complexes (equation 28) or by photoexcitation of a sensitizer substrate (S) in the presence of a suitable donor/acceptor partner (equations 29 and 30). Both techniques result in the formation of a cation radical/radical anion pair. Often the difficulty of overlapping absorption spectra of the cation radical and radical anion hinders detection of the radical anion by optical methods. Another complication in these methods is the efficient back electron transfer in the geminate cation radical/radical anion pair initially formed on ET, which often results in low yields of the free ions. In addition, direct irradiation of a substrate of interest often results in efficient photochemical processes from the excited state (S ) that compete with PET. 

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