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

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

Journal

Doklady Chemistry
ISSN: 0012-5008

Output data

Year: 2022, Volume: 507, Number: 2, Pages: 270-280 Pages count : 11 DOI: 10.1134/s0012500822700148

Authors

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

Affiliations

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

Submitted:	Jul 20, 2022
Published print:	Feb 15, 2023

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

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