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  Magneto-Structural Correlations in a Series of Pseudotetrahedral [CoII(XR)4]2– Single Molecule Magnets: An ab Initio Ligand Field Study

Suturina, E. A., Maganas, D., Bill, E., Atanasov, M., & Neese, F. (2015). Magneto-Structural Correlations in a Series of Pseudotetrahedral [CoII(XR)4]2– Single Molecule Magnets: An ab Initio Ligand Field Study. Inorganic Chemistry, 54(20), 9948-9961. doi:10.1021/acs.inorgchem.5b01706.

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Suturina, Elizaveta A.1, 2, Author           
Maganas, Dimitrios1, Author           
Bill, Eckhard1, Author           
Atanasov, Mihail1, 3, Author           
Neese, Frank1, Author           
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Novosibirsk State University, Pirogova 2, 630090, Novosibirsk, Russia, ou_persistent22              
3Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Akad. Georgi Bontchev Street 11, 1113 Sofia, Bulgaria, ou_persistent22              


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 Abstract: Over the past several decades, tremendous efforts have been invested in finding molecules that display slow relaxation of magnetization and hence act as single-molecule magnets (SMMs). While initial research was strongly focused on polynuclear transition metal complexes, it has become increasingly evident that SMM behavior can also be displayed in relatively simple mononuclear transition metal complexes. One of the first examples of a mononuclear SMM that shows a slow relaxation of the magnetization in the absence of an external magnetic field is the cobalt(II) tetra-thiolate [Co(SPh)4]2–. Fascinatingly, substitution of the donor ligand atom by oxygen or selenium dramatically changes zero-field splitting (ZFS) and relaxation time. Clearly, these large variations call for an in-depth electronic structure investigation in order to develop a qualitative understanding of the observed phenomena. In this work, we present a systematic theoretical study of a whole series of complexes (PPh4)2[Co(XPh)4] (X = O, S, Se) using multireference ab initio methods. To this end, we employ the recently proposed ab initio ligand field theory, which allows us to translate the ab initio results into the framework of ligand field theory. Magneto-structural correlations are then developed that take into account the nature of metal–ligand covalent bonding, ligand spin–orbit coupling, and geometric distortions away from pure tetrahedral symmetry. The absolute value of zero-field splitting increases when the ligand field strength decreases across the series from O to Te. The zero-field splitting of the ground state of the hypothetical [Co(TePh)4]2– complex is computed to be about twice as large as for the well-known (PPh4)2[Co(SPh)4] compound. It is shown that due to the π-anisotropy of the ligand donor atoms (S, Se) magneto-structural correlations in [Co(OPh)4]2– complex differ from [Co(S/SePh)4]2–. In the case of almost isotropic OPh ligand, only variations in the first coordination sphere affect magnetic properties, but in the case of S/SePh ligand, variations in the first and second coordination sphere become equally important for magnetic properties.


Language(s): eng - English
 Dates: 2015-07-282015-10-072015-10-19
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.5b01706
 Degree: -



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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 54 (20) Sequence Number: - Start / End Page: 9948 - 9961 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669