Synthesis of Nitroxide Diradical Using a New Approach
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 <i>tert</i>-butylamide, followed by oxidation of the thusly formed <i>...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/11/2701 |
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| author | Pavel Fedyushin Tatyana Rybalova Nargiz Asanbaeva Elena Bagryanskaya Alexey Dmitriev Nina Gritsan Maxim Kazantsev Evgeny Tretyakov |
| author_facet | Pavel Fedyushin Tatyana Rybalova Nargiz Asanbaeva Elena Bagryanskaya Alexey Dmitriev Nina Gritsan Maxim Kazantsev Evgeny Tretyakov |
| author_sort | Pavel Fedyushin |
| collection | DOAJ |
| description | 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 <i>tert</i>-butylamide, followed by oxidation of the thusly formed <i>N</i>4,<i>N</i>4′-di-<i>tert</i>-butyl-2,2′,3,3′,5,5′,6,6′-octafluorobiphenyl-4,4′-diamine with <i>meta</i>-chloroperoxybenzoic acid, led to the polyfluorinated nitroxide diradical, <i>N</i>,<i>N</i>′-(perfluorobiphenyl-4,4′-diyl)bis(<i>N</i>-<i>tert</i>-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 <i>J</i> from −2.65 to −1.14 cm<sup>−1</sup>. |
| first_indexed | 2024-03-10T19:14:43Z |
| format | Article |
| id | doaj.art-1ec586c707ca495284a8fecd439959f0 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T19:14:43Z |
| publishDate | 2020-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-1ec586c707ca495284a8fecd439959f02023-11-20T03:29:07ZengMDPI AGMolecules1420-30492020-06-012511270110.3390/molecules25112701Synthesis of Nitroxide Diradical Using a New ApproachPavel Fedyushin0Tatyana Rybalova1Nargiz Asanbaeva2Elena Bagryanskaya3Alexey Dmitriev4Nina Gritsan5Maxim Kazantsev6Evgeny Tretyakov7N. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentieva Avenue, 630090 Novosibirsk, RussiaN. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentieva Avenue, 630090 Novosibirsk, RussiaN. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentieva Avenue, 630090 Novosibirsk, RussiaN. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentieva Avenue, 630090 Novosibirsk, RussiaDepartment of Physics, Novosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, RussiaDepartment of Physics, Novosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, RussiaN. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentieva Avenue, 630090 Novosibirsk, RussiaN. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentieva Avenue, 630090 Novosibirsk, RussiaA 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 <i>tert</i>-butylamide, followed by oxidation of the thusly formed <i>N</i>4,<i>N</i>4′-di-<i>tert</i>-butyl-2,2′,3,3′,5,5′,6,6′-octafluorobiphenyl-4,4′-diamine with <i>meta</i>-chloroperoxybenzoic acid, led to the polyfluorinated nitroxide diradical, <i>N</i>,<i>N</i>′-(perfluorobiphenyl-4,4′-diyl)bis(<i>N</i>-<i>tert</i>-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 <i>J</i> from −2.65 to −1.14 cm<sup>−1</sup>.https://www.mdpi.com/1420-3049/25/11/2701fluoroarenesaromatic nucleophilic substitution<i>tert</i>-butylanilinesnitroxidesdiradicals |
| spellingShingle | Pavel Fedyushin Tatyana Rybalova Nargiz Asanbaeva Elena Bagryanskaya Alexey Dmitriev Nina Gritsan Maxim Kazantsev Evgeny Tretyakov Synthesis of Nitroxide Diradical Using a New Approach Molecules fluoroarenes aromatic nucleophilic substitution <i>tert</i>-butylanilines nitroxides diradicals |
| title | Synthesis of Nitroxide Diradical Using a New Approach |
| title_full | Synthesis of Nitroxide Diradical Using a New Approach |
| title_fullStr | Synthesis of Nitroxide Diradical Using a New Approach |
| title_full_unstemmed | Synthesis of Nitroxide Diradical Using a New Approach |
| title_short | Synthesis of Nitroxide Diradical Using a New Approach |
| title_sort | synthesis of nitroxide diradical using a new approach |
| topic | fluoroarenes aromatic nucleophilic substitution <i>tert</i>-butylanilines nitroxides diradicals |
| url | https://www.mdpi.com/1420-3049/25/11/2701 |
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