100045-13-4Relevant articles and documents
Effect of nitroxide radicals on chemically induced dynamic electron polarization of spin-correlated radical pairs in aqueous micellar solutions of sodium dodecyl sulfate
Gorelik,Tarasov,Shakirov,Bagryanskaya
experimental part, p. 1416 - 1427 (2009/09/30)
The multispin systems consisting of spin-correlated radical pairs (SCRPs) and stable nitroxide radicals, localized in micelles of sodium dodecyl sulfate (SDS), were studied by ESR and pulse laser photolysis techniques. In all the systems studied, the stab
Reaction pathways involved in the quenching of the photoactivated aromatic ketones xanthone and 1-azaxanthone by polyalkylbenzenes
Coenjarts,Scaiano
, p. 3635 - 3641 (2007/10/03)
The reactions of the photoexcited aromatic ketones, xanthone and 1-azaxanthone, with polyalkylbenzene donors yields the corresponding ketyl radicals as detected by nanosecond laser flash photolysis. On the basis of formation of these photoreduced products, the quenching of the photoexcited species is expected to occur either by a one-step hydrogen abstraction from the donor, electron transfer followed by proton transfer from the donor, or by formation of a charge-transfer type encounter complex prior to hydrogen atom transfer. The reactions of triplet xanthone and triplet 1-azaxanthone with polyalkylbenzene donors in acetonitrile were investigated to probe the effect of the nature of the triplet state and the redox properties on the relative importance of each quenching pathway. Determination of bimolecular rate constants, as well as analysis of kinetic isotope effects and ketyl radical yields, suggests that for both xanthone and 1-azaxanthone the quenching process is dominated by formation of charge-transfer encounter complexes between excited-state aromatic ketone acceptor and ground-state polyalkylbenzene donor. The reactivites of the xanthone π,π* triplet and 1-azaxanthone n,π* triplet toward these donors is shown to be governed by their reduction potentials, with their electronic configuration being unimportant to the kinetics of encounter complex formation. The only exception to this is found when sterically encumbered polyalkylbenzene donors are employed. Results with these compounds suggest that π,π* and n,π* states form encounter complexes of different structure which affects their ability to react with hindered donors. Additionally, product yields with all of the donors are controlled by both the extent of charge transfer within encounter complexes and the encounter complex structure.
