Abstract
Strong reducing agents, such as phenols and amines, decrease substantially the quantum yield of aromatic ketone consumption in solid polymers. A significant quenching of ketone phosphorescence and an increase in the yield of radical pairs are unambiguous evidence for the efficient primary intermolecular transfer of H atoms under these conditions. The effect in question is related to a sharp change in the ratio of recombination and disproportionation rates of geminate radical pairs in solid polymers in comparison with solutions and micellar systems. The main reason for the phenomenon is the low molecular mobility, which provides no sufficiently fast reorganization of reacting species and their environment needed for the formation of radical pair recombination products.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1403–1406, June, 2005.
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Ivanov, V.B., Kutsenova, A.V. & Khavina, E.Y. Chemical dynamics of radical pairs formed by benzophenone photoreduction in solid polymers. Russ Chem Bull 54, 1445–1448 (2005). https://doi.org/10.1007/s11172-005-0425-y
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DOI: https://doi.org/10.1007/s11172-005-0425-y