Research output: Contribution to journal › Article › peer-review
An approach to fluorinated phthalonitriles containing a nitronyl nitroxide or iminonitroxide moiety. / Fedyushin, Pavel; Panteleeva, Elena; Bagryanskaya, Irina et al.
In: Journal of Fluorine Chemistry, Vol. 217, 01.01.2019, p. 1-7.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - An approach to fluorinated phthalonitriles containing a nitronyl nitroxide or iminonitroxide moiety
AU - Fedyushin, Pavel
AU - Panteleeva, Elena
AU - Bagryanskaya, Irina
AU - Maryunina, Kseniya
AU - Inoue, Katsuya
AU - Stass, Dmitri
AU - Tretyakov, Evgeny
N1 - Publisher Copyright: © 2018 Elsevier B.V.
PY - 2019/1/1
Y1 - 2019/1/1
N2 - A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl lithium derivative was found to react with perfluorophthalonitrile with formation of 2-(3,4-dicyano-2,5,6-trifluorophenyl)- (1) and 2-(2-amino-4,5-dicyano-3,6-difluorophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl (2). The yields of 1 were near 15% independently of reaction time (from 2 to 6 h), whereas the yields of 2 considerably increased from a trace amount to 20%. Both nitronyl nitroxides were reduced to the corresponding iminonitroxides in the presence of NaNO2/AcOH with yields 80–95%. Molecular and crystal structures of the obtained nitroxides were solved by monocrystal X-ray diffraction analysis, and the nature of the radical was ascertained by electron spin spectroscopy (ESR) and SQUID magnetometry. Static magnetochemical measurements of 1 revealed domination of the ferromagnetic exchange interactions between the odd electrons of the paramagnetic centres. The exchange interactions probably proceed via short intermolecular contacts (3.021(3) and 3.05(2) Å) between the nitroxide O atoms and cyanide C atoms. Structural characteristics of the prepared nitroxides make them valuable precursors for the synthesis of paramagnetic macrocycles, which may serve as building blocks in the field of molecular magnetism.
AB - A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl lithium derivative was found to react with perfluorophthalonitrile with formation of 2-(3,4-dicyano-2,5,6-trifluorophenyl)- (1) and 2-(2-amino-4,5-dicyano-3,6-difluorophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl (2). The yields of 1 were near 15% independently of reaction time (from 2 to 6 h), whereas the yields of 2 considerably increased from a trace amount to 20%. Both nitronyl nitroxides were reduced to the corresponding iminonitroxides in the presence of NaNO2/AcOH with yields 80–95%. Molecular and crystal structures of the obtained nitroxides were solved by monocrystal X-ray diffraction analysis, and the nature of the radical was ascertained by electron spin spectroscopy (ESR) and SQUID magnetometry. Static magnetochemical measurements of 1 revealed domination of the ferromagnetic exchange interactions between the odd electrons of the paramagnetic centres. The exchange interactions probably proceed via short intermolecular contacts (3.021(3) and 3.05(2) Å) between the nitroxide O atoms and cyanide C atoms. Structural characteristics of the prepared nitroxides make them valuable precursors for the synthesis of paramagnetic macrocycles, which may serve as building blocks in the field of molecular magnetism.
KW - Fluorinated phthalonitriles
KW - Iminonitroxides
KW - Nitronyl nitroxides
KW - Nucleophilic substitution
KW - X-ray diffraction analysis
KW - SPIN
KW - MAGNETIC INTERACTION
KW - DIARYLETHENE
KW - CHEMISTRY
KW - BOND
KW - FREE-RADICALS
UR - http://www.scopus.com/inward/record.url?scp=85056483552&partnerID=8YFLogxK
U2 - 10.1016/j.jfluchem.2018.10.016
DO - 10.1016/j.jfluchem.2018.10.016
M3 - Article
AN - SCOPUS:85056483552
VL - 217
SP - 1
EP - 7
JO - Journal of Fluorine Chemistry
JF - Journal of Fluorine Chemistry
SN - 0022-1139
ER -
ID: 17472544