A Crystallographic Study of a Novel Tetrazolyl-Substituted Nitronyl Nitroxide Radical
Научная публикация
| Общая информация |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Crystals
, E-ISSN: 2073-4352
|
| Вых. Данные |
Год: 2018,
Том: 8,
Номер: 9,
Номер статьи
: 334,
Страниц
: 7
DOI:
10.3390/cryst8090334
|
| Ключевые слова |
stable radicals; nitronyl nitroxides; tetrazoles; hydrogen bonding; crystal structure;
exchange interaction; density functional theory |
| Авторы |
Romanov Vasily E.
1
,
Bagryanskaya Irina Yu.
1,2
,
Gorbunov Dmitry E.
2,3
,
Gritsan Nina P.
2,3
,
Zaytseva Elena V.
1,2
,
Luneau Dominique
4
,
Tretyakov Evgeny V.
1,2
|
| Организации |
| 1 |
N. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentiev Avenue, Novosibirsk 630090, Russia
|
| 2 |
Novosibirsk State University, 2 Pirogova Str., Novosibirsk 630090, Russia
|
| 3 |
Institute of Chemical Kinetics and Combustion, 3 Institutskaya Str., Novosibirsk 63009, Russia
|
| 4 |
Universit´e Claude Bernard Lyon-1, Campus de La Doua, 69622 Villeurbanne CEDEX, France
|
|
Информация о финансировании (2)
|
1
|
Российский фонд фундаментальных исследований
|
17-53-150020 (АААА-А17-117040510200-1)
|
|
2
|
Российский научный фонд
|
16-13-10155
|
Spin-labelled compounds are widely used in chemistry, physics, biology, and material
sciences, but the directed synthesis of some functionalized organic radicals is still a challenge.
We succeeded in the preparation of a tetrazolyl-substituted nitronyl nitroxide radical in pure
crystalline form. According to the single-crystal X-ray data, intra-(NH . . . O, 2.43 Å) and
inter-molecular hydrogen bonds (NH . . . O, 1.91 Å) are formed between NH groups of the tetrazole
cycles and O atoms of the paramagnetic moieties. The intermolecular H-bonds connect the molecules forming chains along the a-axis. Moreover, there are short intermolecular contacts between the O atoms (3.096 Å) and between the O and C atoms (3.096 Å) of the nitronyl nitroxide moieties within the chain. The spin-unrestricted broken-symmetry calculations performed at the BS-UB3LYP/def2-TZVP level of theory predicted a sufficient ferromagnetic interaction (J ≈ 20 cm–1) between the adjacent radicals inside the chain, but a weak antiferromagnetic interaction (−J ≤0.2 cm−1) between the nearest radicals belonging to the different chains. Thus, a rare case when stable radicals, the tetrazolyl-substituted nitronyl nitroxides, are ordered into ferromagnetic chains was revealed; an investigation of the magneto-structural correlations inherent in the nitroxide radical will demand a special experiment in the sub-Kelvin regime.