Solvent-Induced Encapsulation of Cobalt(II) Ion by a Boron-Capped tris-Pyrazoloximate Full article
Journal |
Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X |
||||||||
---|---|---|---|---|---|---|---|---|---|
Output data | Year: 2020, Volume: 59, Number: 9, Pages: 5845-5853 Pages count : 10 DOI: 10.1021/acs.inorgchem.9b03335 | ||||||||
Tags | BIPYRIDYL LIGANDS; COMPLEXES; IRON(II); PROGRAM; MAGNETS | ||||||||
Authors |
|
||||||||
Affiliations |
|
Funding (4)
1 | Russian Foundation for Basic Research | 18-03-00675 (АААА-А18-118020190244-6) |
2 | Russian Foundation for Basic Research | 18-29-23007 (АААА-А19-119042590091-3) |
3 | Russian Science Foundation | 16-13-10475 (АААА-А16-116041950213-3) |
4 | Council for Grants of the President of the Russian Federation | МК-199.2019.3 |
Abstract:
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.
Cite:
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
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
Dates:
Submitted: | Nov 13, 2019 |
Published online: | Jan 27, 2020 |
Published print: | May 4, 2020 |
Identifiers:
Web of science | WOS:000530668400009 |
Scopus | 2-s2.0-85084761684 |
Elibrary | 43304452 |
Chemical Abstracts | 2020:158622 |
Chemical Abstracts (print) | 172:445034 |
PMID | 31984742 |
OpenAlex | W3004368129 |