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  Tuning Magnetic Anisotropy Through Ligand Substitution in Five-Coordinate Co(II) Complexes

Schweinfurth, D., Krzystek, J., Atanasov, M., Klein, J., Hohloch, S., Telser, J., et al. (2017). Tuning Magnetic Anisotropy Through Ligand Substitution in Five-Coordinate Co(II) Complexes. Inorganic Chemistry, 56(9), 5253-5265. doi:10.1021/acs.inorgchem.7b00371.

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 Creators:
Schweinfurth, David1, Author
Krzystek, J.2, Author
Atanasov, Mihail3, 4, Author           
Klein, Johannes1, Author
Hohloch, Stephan1, Author
Telser, Joshua5, Author
Demeshko, Serhiy6, Author
Meyer, Franc6, Author
Neese, Frank3, Author           
Affiliations:
1Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 34-36, D-14195 Berlin, Germany, ou_persistent22              
2National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States, ou_persistent22              
3Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
4Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria, ou_persistent22              
5Department of Biological, Chemical, and Physical Sciences, Roosevelt University, Chicago, Illinois 60605, United States, ou_persistent22              
6Universität Göttingen, Institut für Anorganische Chemie, Tammanstraße 4, D-37077 Göttingen, Germany, ou_persistent22              

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 Abstract: Understanding the origin of magnetic anisotropy and having the ability to tune it are essential needs of the rapidly developing field of molecular magnetism. Such attempts at determining the origin of magnetic anisotropy and its tuning are still relatively infrequent. One candidate for such attempts are mononuclear Co(II) complexes, some of which have recently been shown to possess slow relaxation of their magnetization. In this contribution we present four different five-coordinated Co(II) complexes, 1–4, that contain two different “click” derived tetradentate tripodal ligands and either Cl or NCS as an additional, axial ligand. The geometric structures of all four complexes are very similar. Despite this, major differences are observed in their electronic structures and hence in their magnetic properties as well. A combination of temperature dependent susceptibility measurements and high-frequency and -field EPR (HFEPR) spectroscopy was used to accurately determine the magnetic properties of these complexes, expressed through the spin Hamiltonian parameters: g-values and zero-field splitting (ZFS) parameters D and E. A combination of optical d-d absorption spectra together with ligand field theory was used to determine the B and Dq values of the complexes. Additionally, state of the art quantum chemical calculations were applied to obtain bonding parameters and to determine the origin of magnetic anisotropy in 1–4. This combined approach showed that the D values in these complexes are in the range from −9 to +9 cm–1. Correlations have been drawn between the bonding nature of the ligands and the magnitude and sign of D. These results will thus have consequences for generating novel Co(II) complexes with tunable magnetic anisotropy and hence contribute to the field of molecular magnetism.

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Language(s): eng - English
 Dates: 2017-02-092017-04-122017-05-01
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.7b00371
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 56 (9) Sequence Number: - Start / End Page: 5253 - 5265 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669