Adamantyl-Substituted Triplet Diradical: Synthesis, Structure, Redox and Magnetic Properties

Adamantyl-Substituted Triplet Diradical: Synthesis, Structure, Redox and Magnetic Properties Научная публикация

Журнал

Doklady Chemistry
ISSN: 0012-5008

Вых. Данные

Год: 2022, Том: 507, Номер: 2, Страницы: 270-280 Страниц : 11 DOI: 10.1134/s0012500822700148

Авторы

Mikhailova M.V. ¹ , Dudko E.M. ^1,2 , Nasyrova D.I. ¹ , Akyeva A.Ya. ¹ , Syroeshkin M.A. ¹ , Bogomyakov A.S. ³ , Artyukhova N.A. ³ , Fedin M.V. ³ , Gorbunov D.E. ⁴ , Gritsan N.P. ⁴ , Tretyakov E.V. ¹ , Ovcharenko V.I. ^1,3 , Egorov M.P. ¹

Организации

1	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991, Moscow, Russia
2	National Research University Higher School of Economics, 101000, Moscow, Russia
3	Institute “International Tomographic Center,” Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk, Russia
4	Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk, Russia

A stable diradical 2-{N-[(3s,5s,7s)-adamantyl-1]-N-oxylamino}-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl—a heteroatomic analogue of trimethylenemethane—has been synthesized by reacting lithiated 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl with 1-nitroso-adamantane, followed by oxidation of the intermediate hydroxylamine. According to X-ray diffraction data, the dihedral angle between the planes of paramagnetic moieties in the paramagnet is close to 60°. Magnetochemical measurements have shown that the energy gap between the triplet and singlet states (2J/kB; H = –2JS1/2S1/2) in the diradical is 880 K. The EPR spectrum of the diradical was simulated using the parameters: S = 1, gxx = 2.007, gyy = 2.005, gzz = 2.006, D = 825 MHz, E = 60 MHz. According to the data of cyclic voltammetry in the anodic region, the diradical undergoes electrochemical oxidation at potentials of 0.79, 1.63, 1.89, and 2.25 V, the first process being chemically and electrochemically reversible. In the cathodic region, the diradical is reduced quasi-reversibly at –1.18 and irreversibly at –2.59 V.

Mikhailova M.V. , Dudko E.M. , Nasyrova D.I. , Akyeva A.Y. , Syroeshkin M.A. , Bogomyakov A.S. , Artyukhova N.A. , Fedin M.V. , Gorbunov D.E. , Gritsan N.P. , Tretyakov E.V. , Ovcharenko V.I. , Egorov M.P.
Adamantyl-Substituted Triplet Diradical: Synthesis, Structure, Redox and Magnetic Properties
Doklady Chemistry. 2022. V.507. N2. P.270-280. DOI: 10.1134/s0012500822700148 WOS Scopus OpenAlex

Поступила в редакцию:	20 июл. 2022 г.
Опубликована в печати:	15 февр. 2023 г.

Web of science:	WOS:000938807600002
Scopus:	2-s2.0-85148478637
OpenAlex:	W4320926551

БД	Цитирований
Scopus	5
Web of science	5