You need JavaScript to view this

E. P. R. spectroscopic study of nitroxide mono- and bi-radicals; Etude par spectroscopie de resonance paramagnetique electronique de monoradicaux et de biradicaux nitroxydes

Abstract

A nitroxide is a molecule containing the group N-O where the oxygen atom made only one bond instead of the usual two. The main advantage of these radicals is their exceptional stability; this allows the study of well defined chemical structures while varying at will the experimental conditions. Studies by electron paramagnetic resonance of nitroxide mono-radicals have given the principal directions and the principal values of the electron-nitrogen nucleus hyperfine tensor and of the anisotropic g-factor tensor. The results were then related to the electronic structure of radicals. An understanding was obtained of the influence of the solvent on the principal values of the tensors, and the marked differences observed in the broadening of hyperfine lines when the medium become viscous. In the nitroxide biradicals, the hyperfine spectra depends not only on the magnetic interactions relative to each monomer, but also on the magnitude of the exchange interaction between the singlet and the triplet states of the dimer; the biradicals studied here are the first organic compounds which show clearly the influence of this exchange on the hyperfine structure. The two unpaired electrons also interact by a magnetic dipolar interaction: in the intermediate case, this can be used to derive  More>>
Authors:
Lemaire, H [1] 
  1. Commissariat a l'Energie Atomique, Grenoble, 38 (France). Centre d'Etudes Nucleaires
Publication Date:
Jul 01, 1967
Product Type:
Thesis/Dissertation
Report Number:
CEA-R-3119
Resource Relation:
Other Information: TH: These docteur es-sciences physiques; 123 refs; PBD: 1967
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ANISOTROPY; ELECTRON SPIN RESONANCE; ELECTRON-ELECTRON INTERACTIONS; ELECTRONIC STRUCTURE; HYPERFINE STRUCTURE; LANDE FACTOR; RADICALS; SENSITIVITY; VISCOSITY
OSTI ID:
20626207
Research Organizations:
CEA Grenoble, 38 (France); Faculte des Sciences de l'Universite de Grenoble, 38 (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
TRN: FR05R3119069320
Availability:
Available from INIS in electronic form
Submitting Site:
FRN
Size:
59 pages
Announcement Date:
Aug 28, 2005

Citation Formats

Lemaire, H. E. P. R. spectroscopic study of nitroxide mono- and bi-radicals; Etude par spectroscopie de resonance paramagnetique electronique de monoradicaux et de biradicaux nitroxydes. France: N. p., 1967. Web.
Lemaire, H. E. P. R. spectroscopic study of nitroxide mono- and bi-radicals; Etude par spectroscopie de resonance paramagnetique electronique de monoradicaux et de biradicaux nitroxydes. France.
Lemaire, H. 1967. "E. P. R. spectroscopic study of nitroxide mono- and bi-radicals; Etude par spectroscopie de resonance paramagnetique electronique de monoradicaux et de biradicaux nitroxydes." France.
@misc{etde_20626207,
title = {E. P. R. spectroscopic study of nitroxide mono- and bi-radicals; Etude par spectroscopie de resonance paramagnetique electronique de monoradicaux et de biradicaux nitroxydes}
author = {Lemaire, H}
abstractNote = {A nitroxide is a molecule containing the group N-O where the oxygen atom made only one bond instead of the usual two. The main advantage of these radicals is their exceptional stability; this allows the study of well defined chemical structures while varying at will the experimental conditions. Studies by electron paramagnetic resonance of nitroxide mono-radicals have given the principal directions and the principal values of the electron-nitrogen nucleus hyperfine tensor and of the anisotropic g-factor tensor. The results were then related to the electronic structure of radicals. An understanding was obtained of the influence of the solvent on the principal values of the tensors, and the marked differences observed in the broadening of hyperfine lines when the medium become viscous. In the nitroxide biradicals, the hyperfine spectra depends not only on the magnetic interactions relative to each monomer, but also on the magnitude of the exchange interaction between the singlet and the triplet states of the dimer; the biradicals studied here are the first organic compounds which show clearly the influence of this exchange on the hyperfine structure. The two unpaired electrons also interact by a magnetic dipolar interaction: in the intermediate case, this can be used to derive the sign of the exchange interaction if the bi-radical is studied in a liquid crystal. Just as for mono-radicals, the hyperfine spectra of bi-radicals show selective broadening in viscous media, which is caused by an overall motional modulation of the anisotropic tensors. This gives another way to determine the sign of the exchange interaction. (author) [French] On appelle nitroxyde une molecule contenant le groupement N-O ou l'atome d'oxygene n'a satisfait qu'une seule liaison de valence sur les deux qui lui sont habituelles. L'interet majeur de ces radicaux reside dans leur exceptionnelle stabilite, permettant ainsi de faire varier a loisir les conditions experimentales d'etude de produits parfaitement bien definis au point de vue structure chimique. L'etude par resonance paramagnetique electronique de monoradicaux nitroxydes conduit a la determination des axes et des elements du tenseur d'interaction hyperfine electron-noyau d'azote et du tenseur d'anisotropie du facteur de Lande: les resultats sont relies a la structure electronique des radicaux. On interprete qualitativement l'influence du solvant sur les elements des tenseurs, ainsi que les elargissements selectifs des raies hyperfines en milieu visqueux. Dans les biradicaux nitroxydes, la structure hyperfine depend non seulement des interactions magnetiques propres a chaque monomere, mais egalement de la grandeur de l'interaction d'echange separant les etats singulet et triplet du dimere; les biradicaux etudies ici sont les premiers composes organiques pour lesquels l'influence de l'echange sur la structure hyperfine est clairement mise en evidence. La presence de deux electrons non apparies introduit egalement une interaction magnetique dipolaire electron-electron, que l'on peut mettre a profit, dans le cas d'un echange intermediaire, pour determiner le signe de l'echange en etudiant le biradical dans un cristal liquide. Ces composes presentent egalement des elargissements selectifs de transitions hyperfines lorsque la viscosite du solvant croit. La theorie utilisee pour interpreter les largeurs de raie des monoradicaux est etendue au cas des biradicaux; elle rend compte des resultats experimentaux si l'on introduit simultanement les anisotropies des facteurs de Lande et des interactions dipolaires electrons-noyaux et electron-electron, en conduisant a une autre determination du signe de l'echange. (auteur)}
place = {France}
year = {1967}
month = {Jul}
}