Magnetic anisotropy and structural flexibility in the f ield-induced single ion magnets [Co{(OPPh2) (EPPh2)N}2], E = S, Se, explored by experimental and computational methods
Abstract
During the last few years, a large number of mononuclear Co(II) complexes of various coordination geometries have been explored as potential single ion magnets (SIMs). In the work presented herein, the Co(II) S = 3/2 tetrahedral [Co{(OPPh2)(EPPh2)N}2], E = S, Se, complexes (abbreviated as CoO2E2), bearing chalcogenated mixed donor-atom imidodiphosphinato ligands, were studied by both experimental and computational techniques. Specifically, direct current (DC) magnetometry provided estimations of their zerof ield splitting (zfs) axial (D) and rhombic (E) parameter values, which were more accurately determined by a combination of far-infrared magnetic spectroscopy and high-frequency and-field EPR spectroscopy studies. The latter combination of techniques was also implemented for the S = 3/2 tetrahedral [Co Received 14th October 2022, Accepted 14th January 2023 DOI: 10.1039/d2dt03335f rsc.li/dalton Introduction {(EPiPr2)2N}2], E = S, Se, complexes, confirming the previously determined magnitude of their zfs parameters. For both pairs of complexes (E = S, Se), it is concluded that the identity of the E donor atom does not significantly affect their zfs parameters. High-resolution multifrequency EPR studies of CoO2E2 provided evidence of multiple conformations, which are more clearly observed for CoO2Se2, in agreement with the structural disorder previously established for this complex by X-ray crystallography. The CoO2E2 complexes were shown to be field-induced SIMs, i.e., they exhibit slow relaxation of magnetization in the presence of an external DC magnetic field. Advanced quantum-chemical calculations on CoO2E2 provided additional insight into their electronic and structural properties.
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- DOI:
- Digital Object Identifier (open in new tab) 10.1039/D2DT03335F
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- Category:
- Articles
- Type:
- artykuły w czasopismach
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DALTON TRANSACTIONS
no. 52,
pages 2036 - 2050,
ISSN: 1477-9226 - Language:
- English
- Publication year:
- 2023
- Bibliographic description:
- Ferentinos E., Tzeli D., Sottini S., Groenen E. J., Ozerov M., Poneti G., Kaniewska-Laskowska K., Krzystek J., Kyritsis P.: Magnetic anisotropy and structural flexibility in the f ield-induced single ion magnets [Co{(OPPh2) (EPPh2)N}2], E = S, Se, explored by experimental and computational methods// DALTON TRANSACTIONS -Vol. 52,iss. 7 (2023), s.2036-2050
- DOI:
- Digital Object Identifier (open in new tab) 10.1039/d2dt03335f
- Sources of funding:
- Verified by:
- Gdańsk University of Technology
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