An ESR study of the cation radicals of azodibenzothiazolyls

Methyl and ethyl derivatives of thiobenzothiazole and their quaternary salts were prepared by the sealed glass tube method. Azinodibenzothiazoles were oxidized by lead(IV) acetate, giving cation radical salts with the boron tetrafluoride anion moiety. The well-resolved esr spectra observed were analyzed by comparing the data with those of a deuteriomethylated radical and with those from the MO calculations. Spin density distribution was consistently determined by computer simulation, including almost the same unpaired electron distribution on the four nitrogen atoms.     

ESR/DFT study of bis-iminophosphorane cation radicals

Bis-iminophosphoranes containing various types of linkers between two R3P==N moieties were electrochemically oxidized at controlled potential in situ in the electron spin resonance (ESR) cavity. For linkers constituted of phenylenes, conjugated phenylenes or merely a dicyanoethylenic bond, this oxidation led to well-resolved ESR spectra which were characterized by their g values and by their 1H, 14N and 31P isotropic hyperfine constants. These coupling constants agree with those calculated by DFT for the corresponding cation radicals. Experimental and theoretical results clearly indicate that in these species the unpaired electron is mostly delocalized on the bridge and on the nitrogen atoms while the spin density on the phosphorus atoms is particularly small. Cyclic voltammetry and ESR spectra show that the nature of the bridge between the two iminophosphoranes considerably influences the oxidation potential of the compound as well as the stability of the radical cation. Information about the conformation of the precursor containing two Ph3P==N moieties separated by a --C(CN)==C(CN)--group was obtained from its crystal structure.     

ESR spectroscopy of the C60 cation produced by photoinduced electron transfer

In this study the existence of the C60 cation produced by photochemically induced electron transfer in the presence of different sensitising molecules is proved for the first time by using ESR spectroscopy. It is demonstrated for triphenylpyryliumtetrafluoroborate (TPP) by this spectroscopic method that the electron transfer from C60 to TPP occurs without an application of a cosensitiser. Furthermore it is shown that the addition of alcohols causes a new radical in the system C60/TPP. The stationary concentration of the C60 cation diminishes even in the presence of a cosensitiser to such a low concentration that it is not detectable by ESR spectrosopy. The spectroscopic study of the sensitiser/C60 system is also extended to the reaction products.     

Kinetics and CIDEP of radicals during photoreduction of acetone with 2-propanol by effect modulated ESR spectroscopy

ESR spectroscopy with modulated radical initiation is used to analyze quantitatively chemical lifetimes and CIDEP enhancements of 2-propyl-2-ol radicals, formed by photoreduction of acetone with 2-propanol in aqueous solution at T = 16°C. The bimolecular termination rate constant of the radicals is found to be diffusion controlled and to depend on the hyperfine state as a consequence of T₀---S mixing in F-pairs. CIDEP enhancements built up in geminate and in F-pairs are separated. Their relative dependence on the hyperfine state agrees with microscopic theory, which however, fails to reproduce the absolute enhancements by a factor of 4. The polarizations indicate equal reactivities towards photoreduction for the three sublevels of the ³nπ* state of acetone, and conservation of the electron spin polarization upon radical formation. The initial separation of the species in the geminate pair is found to lie within the strong exchange region, since geminate and F-pairs show equal RPM polarizations. The CIDEP enhancements limit the rate constant k₂₂ for abstraction of the hydroxylic hydrogen of 2-propanol by ³nπ* acetone to k₂₂ < 10⁵ dm³ mol⁻¹ s ⁻¹.     

Photochemistry of cation radicals in solution : photoinduced oxidation by the phenothiazine cation radical

Irradiation of phenothiazine cation radical, Ph^.+, with 1,1-diphenylethylene, DPE, causes its reduction to Ph and oxidation of DPE. Cyclodimeric products are formed from DPE^.+.     

Kinetics of the reduction of organic cations by cation radicals

It has been found that the reduction of substituted diazonium, iodonium, and tropylium salts by cation radicals of tetra-tert-butyl-bis-pyrylium, tetramethyl-p-phenylene diamine (I), tetraphenylbenzidine, and N-methylphenothiazine obey the kinetic equation of the second order and that it follows an electron transfer mechanism. The logarithms of the rate constants of these reactions decrease with increasing standard free energy of the electron transfer reaction. The rate of the reaction of C₆H₅N₂₊ BF₄ ^– with I and the selectivity of the reactions of the substituted diazonium salts with I increases with the electron donor capacity of the solvent. The addition of crown-ethers accelerates the reaction. The reaction rate increases also with increasing ionic strength of the solution, whereby the Cl^– anions have a specifically accelerating effect. The observed rules governing the influence of the medium contradict those found earlier for the interaction of organic cations with neutral radicals and anion radicals. This is attributed to the fact that the electron transfer takes place in ternary complexes cation-solvent (crown ether, Cl^– ion)-cation radical.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 1, pp. 45–51, January–February, 1985.The authors wish to express their gratitude to V. V. Lobonov for tje performance of the quantum chemical calculations.     

ESR investigation of sucrose radicals produced by particle irradiation

We investigated sucrose radicals produced by heavy-ion irradiation with various linear energy transfer (LETs) and the possibility for a sucrose electron spin resonance (ESR) dosimeter. The impact of heavy ions on sucrose produced sucrose radicals, which were measured by ESR. The obtained spectral pattern was the same as that for helium (He) ions, carbon (C) ions, neon (Ne) ions, iron (Fe) ions, and gamma-ray irradiation. Identical spectra were measured after 1 year, but the initial intensities decreased by a few percent when the samples were kept in ESR tubes with the caps at ambient temperature. The total spin concentration obtained by heavy-ion irradiation had a linear relation with the absorbed dose, and correlated logarithmically with the LET. Qualitative ESR analyses showed that the production of sucrose radicals depended on both the particle identity and the LET at the same dose. The production of spin concentration by He ions was the most sensitive to LET. Empirical relations between the LET and the spin yield for various particles imply that the LET at a certain dose can be estimated by the spin concentration. Therefore, the present ESR results imply that sucrose can be used to monitor the absorbed dose and the LET of particle irradiation.     

High-resolution IR cavity ring-down spectroscopy of jet-cooled free radicals and other species

Initial spectral results are reported from a newly constructed cavity ringdown spectrometer. The apparatus incorporates a slit-jet expansion, with or without a discharge, to produce cold sample molecules. High spectral resolution in both the near- and mid-IR is obtained by using stimulated Raman scattering of the pulsed amplified output of a cw Ti:Sa ring laser. Molecular spectra presented include the electronic near-IR transitions a (1)Delta(g)(-)<-- X (3)Sigma(g)(-) of O(2) and B (3)Pi(g)<-- A (3)Sigma(u)(+) of metastable N(2) and vibrational overtones of H(2)O (polyad 2) and the OH radical. Fundamental vibrational transitions of CH(3) (nu(3)) in the mid-IR are also observed. This apparatus has demonstrated the potential for obtaining high-resolution spectra of both reactive and non-reactive species throughout the entire IR region.     

ESR spin-trapping study of radicals produced by donor-acceptor interactions

Nitroso compounds, well known as spin traps, have not been applied for scavenging free radicals formed in reactions with the contribution of chloranil, so far. In our studies we show that spin traps such as nitrosodurene (ND), 2,6-dichloronitrosobenzene (Cl₂NB) react with radicals formed in the reaction between chloranil and durene, yielding stable spin adducts.

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ESR Spectra of radicals produced by reduction of pyridine and pyrazine

Radicals produced by reaction of e^?_aq with pyridine, pyrazine, and pyrazinedicarboxylic acid have been studied by electron spin resonance using the in situ radiolysis steady-state ESR technique. The radical anions initially produced have been found to undergo rapid protonation on nitrogen to form pyridinyl and pyrazinyl radicals. The NH proton of pyridinyl radical does not dissociate even at pH 13.7. The radical from pyrazine has been observed only in the doubly protonated positively charged form in acid and neutral solutions, but no spectrum was observed in alkaline media. With 2,3-pyrazinedicarboxylic acid the doubly protonated radical has been observed at pH 4–8 and the singly protonated one at pH 11–12. The pK for this dissociation is 9.2. The hyperfine constants of the pyridinyl radical are compared with those obtained from INDO molecular orbital calculations.     

Using ESR spectroscopy to study radical intermediates in proton-exchange membranes exposed to oxygen radicals

Direct ESR and spin-trapping experiments were used to study the behavior of Nafion, a perfluorinated ionomer membrane used in fuel cells, when exposed in the laboratory to oxygen radicals produced by Fenton and photo-Fenton reactions. DMPO (5,5-dimethyl-1-pyroline) was used as the spin trap. The results suggest that the two ESR methods provide complementary information on Nafion fragmentation. The presence of membrane-derived fragments was suggested indirectly by the presence of a broad signal (line width ≈ 84 G) after prolonged exposure of the membrane to the Fenton reagent based on Ti(III), and by the DMPO adduct of a carbon-centered radical in the spin-trapping experiments. The most convincing proof for the presence of perfluorinated radicals was obtained in Nafion membranes partially neutralized by Cu(II), Fe(II) and Fe(III) upon exposure to UV-irradiation in the presence or absence of H₂O₂ (photo-Fenton treatment). Identification of the chain-end radical RCF₂CF ₂ ^• with magnetic parameters different to those determined for the chain-end detected in γ-irradiated Teflon, was taken as evidence for the attack of reactive oxygen radicals on the side-chain of the membrane. Additional support for this suggestion was the detection of the “quartet” ESR signal assigned to the CF₃C^•O radical, and of the “quintet” ESR signal assigned to the radical centered at the intersection of the main and side chains. The limitations and advantages of each approach are discussed.     

ESR spectra and the behavior of substituted indophenoxyl radicals

ESR spectra and structure are compared for radicals formed from substituted indophenols by oxidation (substituents CH₃, i-C₃H₇, t-C₄H₉, t-C₅H₁₁, cyclohexyl). The unpaired electron interacts with the nitrogen and with the hydrogen in the ortho and meta positions of both benzene rings. A kinetic equation of first order with respect to the indophenol applies to the reaction of the latter with benzoyl peroxide. The loss of indophenoxyl radicals in benzene obeys an equation of second order in the radical concentration. The rate constants for radicals with various substituents indicate the radical stability, which falls greatly in going from ones with ortho-t-alkyl substituents to ones with less highly branched groups.     

ESR of cationic isoalloxazine free radicals

The ESR spectra in solution of a number of cationic isoalloxazine free radicals were recorded and interpreted in terms of hyperfine coupling constants. Two previously published interpretations are shown to be incorrect.     

ESR spectra of phosphorus-containing tetrazonyl radicals

Conclusion The oxidation of the products of the reaction of dialkylphosphorylacetaldehydes with aryldiazonium salts gives tetrazonyl radicals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1168–1169, May, 1987.