Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Synthesis of Nitroxide Diradical Using a New Approach. / Fedyushin, Pavel; Rybalova, Tatyana; Asanbaeva, Nargiz и др.
в: Molecules (Basel, Switzerland), Том 25, № 11, 2701, 11.06.2020.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Synthesis of Nitroxide Diradical Using a New Approach
AU - Fedyushin, Pavel
AU - Rybalova, Tatyana
AU - Asanbaeva, Nargiz
AU - Bagryanskaya, Elena
AU - Dmitriev, Alexey
AU - Gritsan, Nina
AU - Kazantsev, Maxim
AU - Tretyakov, Evgeny
N1 - Publisher Copyright: © 2020 by the authors. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2020/6/11
Y1 - 2020/6/11
N2 - A new synthetic pathway to diradical organic systems is proposed. The effectiveness of this approach was exemplified by the synthesis of a new nitroxide diradical. An interaction of perfluorobiphenyl with lithium tert-butylamide, followed by oxidation of the thusly formed N4,N40di-tert-butyl-2,20,3,30,5,50,6,60-octafluorobiphenyl-4,40-diamine with meta- chloroperoxybenzoic acid, led to the polyfluorinated nitroxide diradical, N,N0-(perfluorobiphenyl-4,40-diyl)bis(Ntert-butyl(oxyl)amine), with a good total yield. The polyfluorinated diradical is stable and can be isolated in free form and completely characterized. The structure of the nitroxide diradical was proved by single-crystal X-ray diffraction analysis. According to the X-ray diffraction data, the diradical is considerably twisted: dihedral angles between the planes of the nitroxide groups and aromatic cycles are 65.1◦ and 69.5◦, and between aromatic cycles 52.6◦. Quantum chemical calculations predict well-balanced size of both intramolecular and intermolecular exchange interactions with J from −2.65 to −1.14 cm−1
AB - A new synthetic pathway to diradical organic systems is proposed. The effectiveness of this approach was exemplified by the synthesis of a new nitroxide diradical. An interaction of perfluorobiphenyl with lithium tert-butylamide, followed by oxidation of the thusly formed N4,N40di-tert-butyl-2,20,3,30,5,50,6,60-octafluorobiphenyl-4,40-diamine with meta- chloroperoxybenzoic acid, led to the polyfluorinated nitroxide diradical, N,N0-(perfluorobiphenyl-4,40-diyl)bis(Ntert-butyl(oxyl)amine), with a good total yield. The polyfluorinated diradical is stable and can be isolated in free form and completely characterized. The structure of the nitroxide diradical was proved by single-crystal X-ray diffraction analysis. According to the X-ray diffraction data, the diradical is considerably twisted: dihedral angles between the planes of the nitroxide groups and aromatic cycles are 65.1◦ and 69.5◦, and between aromatic cycles 52.6◦. Quantum chemical calculations predict well-balanced size of both intramolecular and intermolecular exchange interactions with J from −2.65 to −1.14 cm−1
KW - aromatic nucleophilic substitution
KW - diradicals
KW - fluoroarenes
KW - nitroxides
KW - tert-butylanilines
KW - DESIGN
KW - TRIPLET
KW - NITRONYL NITROXIDE
KW - COMPLEXES
KW - RADICALS
KW - MAGNETIC-PROPERTIES
KW - GROUND-STATES
KW - Models, Chemical
KW - Nitrogen Oxides/chemical synthesis
KW - Quantum Dots
KW - X-Ray Diffraction
KW - Halogenation
KW - Molecular Structure
UR - http://www.scopus.com/inward/record.url?scp=85086623729&partnerID=8YFLogxK
U2 - 10.3390/molecules25112701
DO - 10.3390/molecules25112701
M3 - Article
C2 - 32545156
AN - SCOPUS:85086623729
VL - 25
JO - Molecules
JF - Molecules
SN - 1420-3049
IS - 11
M1 - 2701
ER -
ID: 24537804