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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 Совет по грантам Президента Российской Федерации МК-199.2019.3

Реферат: 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.
Библиографическая ссылка: Belov A.S. , Voloshin Y.Z. , Pavlov A.A. , Nelyubina Y.V. , Belova S.A. , Zubavichus Y.V. , Avdeeva V.V. , Efimov N.N. , Malinina E.A. , Zhizhin K.Y. , Kuznetsov N.T.
Solvent-Induced Encapsulation of Cobalt(II) Ion by a Boron-Capped tris-Pyrazoloximate
Inorganic Chemistry. 2020. V.59. N9. P.5845-5853. DOI: 10.1021/acs.inorgchem.9b03335 WOS Scopus РИНЦ
Даты:
Поступила в редакцию: 13 нояб. 2019 г.
Опубликована online: 27 янв. 2020 г.
Опубликована в печати: 4 мая 2020 г.
Идентификаторы:
Web of science WOS:000530668400009
Scopus 2-s2.0-85084761684
РИНЦ 43304452
Chemical Abstracts 2020:158622
Альметрики: