Synthesis of Nitroxide Diradical Using a New Approach

Synthesis of Nitroxide Diradical Using a New Approach Full article

Journal

Molecules
, E-ISSN: 1420-3049

Output data

Year: 2020, Volume: 25, Number: 11, Article number : 2701, Pages count : DOI: 10.3390/molecules25112701

Tags

fluoroarenes; aromatic nucleophilic substitution; tert-butylanilines; nitroxides; diradicals

Authors

Fedyushin Pavel ¹ , Rybalova Tatyana ¹ , Asanbaeva Nargiz ^1,2 , Bagryanskaya Elena ^1,2 , Dmitriev Alexey ^2,3 , Gritsan Nina ^2,3 , Kazantsev Maxim ^1,4 , Tretyakov Evgeny ^1,4

Affiliations

1	(Данные Web of science) NN Vorozhtsov Inst Organ Chem, 9 Ac Lavrentieva Ave, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Dept Phys, 2 Pirogova Str, Novosibirsk 630090, Russia
3	(Данные Web of science) VV Voevodski Inst Chem Kinet & Combust, 3 Inst Skaya Str, Novosibirsk 630090, Russia
4	(Данные Web of science) Novosibirsk State Univ, Dept Nat Sci, 2 Pirogova Str, Novosibirsk 630090, Russia

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,N4 ' -di-tert-butyl-2,2 ' ,3,3 ' ,5,5 ' ,6,6 ' -octafluorobiphenyl-4,4 ' -diamine with meta-chloroperoxybenzoic acid, led to the polyfluorinated nitroxide diradical, N,N '-(perfluorobiphenyl-4,4 ' -diyl)bis(N-tert-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 degrees and 69.5 degrees, and between aromatic cycles 52.6 degrees. Quantum chemical calculations predict well-balanced size of both intramolecular and intermolecular exchange interactions with J from -2.65 to -1.14 cm(-1).

Fedyushin P. , Rybalova T. , Asanbaeva N. , Bagryanskaya E. , Dmitriev A. , Gritsan N. , Kazantsev M. , Tretyakov E.
Synthesis of Nitroxide Diradical Using a New Approach

Molecules. 2020. V.25. N11. 2701 . DOI: 10.3390/molecules25112701 WOS Scopus РИНЦ

Full text from publisher

Published online:

Jun 11, 2020

Web of science	WOS:000553858800238
Scopus	2-s2.0-85086623729
Elibrary	43301608
OpenAlex	W3035633132