Solvent-Induced Encapsulation of Cobalt(II) Ion by a Boron-Capped tris-Pyrazoloximate
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Inorganic Chemistry
ISSN: 0020-1669
, E-ISSN: 1520-510X
|
| Вых. Данные |
Год: 2020,
Том: 59,
Номер: 9,
Страницы: 5845-5853
Страниц
: 10
DOI:
10.1021/acs.inorgchem.9b03335
|
| Ключевые слова |
BIPYRIDYL LIGANDS; COMPLEXES; IRON(II); PROGRAM; MAGNETS |
| Авторы |
Belov Alexander S.
1
,
Voloshin Yan Z.
1,2
,
Pavlov Alexander A.
1
,
Nelyubina Yulia V.
1,2
,
Belova Svetlana A.
1
,
Zubavichus Yan V.
3,4
,
Avdeeva Varvara V.
2
,
Efimov Nikolay N.
2
,
Malinina Elena A.
2
,
Zhizhin Konstantin Yu.
2
,
Kuznetsov Nikolay T.
2
|
| Организации |
| 1 |
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova st., Moscow, 119991, Russia
|
| 2 |
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., Moscow, 119991, Russia
|
| 3 |
National Research Centre “Kurchatov Institute”, 1 Kurchatova pl., Moscow, 123182, Russia
|
| 4 |
Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences, 5 Lavrentiev Ave., 630090 Novosibirsk, Russia
|
|
Информация о финансировании (4)
|
1
|
Российский фонд фундаментальных исследований
|
18-03-00675 (АААА-А18-118020190244-6)
|
|
2
|
Российский фонд фундаментальных исследований
|
18-29-23007 (АААА-А19-119042590091-3)
|
|
3
|
Российский научный фонд
|
16-13-10475 (АААА-А16-116041950213-3)
|
|
4
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Совет по грантам Президента Российской Федерации
|
МК-199.2019.3
|
Boron-cross-linked cobalt(II) pseudoclathrochelate was obtained by the template reaction of 2-acetylpyrazoloxime, phenylboronic acid, and a new DMF cobalt(II) solvato complex with a decachloro-closo-decaborate dianion. As confirmed by single-crystal X-ray diffraction, this complex crystallizes with two symmetry-independent cobalt(II) pseudoclathrochelate cations, one decachloro-closo-decaborate dianion, one benzene, one dichloromethane solvent molecule, and two molecules of DMF. The latter act as pseudocapping fragments to the monocapped tris-pyrazoloximate ligands by forming N–H···O hydrogen bonds with their pyrazole groups. The CoIIN6-coordination polyhedra adopt a nearly ideal TP geometry with distortion angles φ equal to 1.22(16) and 2.58(17)° for two symmetry-independent pseudoclathrochelate cations, both containing the encapsulated cobalt(II) ion in its high-spin state (Co–N 2.115(4)–2.198(3) Å). Magnetic properties of this complex were studied both by dc-magnetometry and by solution-state NMR spectroscopy to reveal a high magnetic anisotropy, thus suggesting a large magnetic susceptibility tensor anisotropy (25.8 × 10–32 m3 at 298 K) and a large negative zero-field splitting energy (−85 cm–1). The results of magnetometry studies in the ac magnetic field suggest a single molecule magnet behavior of this TP complex with an effective magnetization reversal barrier of approximately 130 cm–1. Its pseudocapping DMF molecules that form H-bonds with tris-pyrazoloximate fragments are easy to substitute by strong H-bond acceptors, such as chloride ions and di- and tetramethylureas, thus affecting the magnetic properties of a whole pseudomacrobicyclic paramagnetic system.