Switched external magnetic field CIDNP studies of coupling reaction of carbon-centered radicals with TEMPO

Literature Information

Publication Date 2004-03-31
DOI 10.1039/B401093K
Impact Factor 3.676
Authors

N. V. Lebedeva, D. P. Zubenko, E. G. Bagryanskaya, R. Z. Sagdeev, G. S. Ananchenko, S. Marque, D. Bertin, P. Tordo


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Abstract

CIDNP in a switched external magnetic field (SEMF) is applied to study reactions of carbon-centered radicals with the persistent nitroxyl radical TEMPO (2,2,6,6-tetramethylpiperidinyl-N-oxyl) in benzene. The carbon-centered radicals were generated by laser pulse photolysis of the corresponding ketone precursors RC(O)R with well-known photochemistry in the presence of TEMPO. Theoretical background of SEMF CIDNP was adapted to the system under study and the analytical solution of the corresponding set of kinetic equations was found. In the case of low initial concentration of radicals R the SEMF CIDNP kinetics are expected to be monoexponential with decay equal to kc[Y] + 1/T1, where kc — coupling rate constant between alkyl and nitroxyl radicals, [Y] — concentration of nitroxyl radicals, and T1 — electron-nuclear relaxation time of transient radicals. Analysis of SEMF CIDNP kinetics with varied concentrations of nitroxide allowed us to derive the corresponding kc values, which were compared with the results of laser flash photolysis experiments found in the literature. Good agreement between different methods is achieved.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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