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  Magneto-Structural Correlations in Pseudotetrahedral Forms of the [Co(SPh)4]2– Complex Probed by Magnetometry, MCD Spectroscopy, Advanced EPR Techniques, and ab Initio Electronic Structure Calculations

Suturina, E. A., Nehrkorn, J., Zadrozny, J. M., Liu, J., Atanasov, M., Weyhermüller, T., et al. (2017). Magneto-Structural Correlations in Pseudotetrahedral Forms of the [Co(SPh)4]2– Complex Probed by Magnetometry, MCD Spectroscopy, Advanced EPR Techniques, and ab Initio Electronic Structure Calculations. Inorganic Chemistry, 56(5), 3102-3118. doi:10.1021/acs.inorgchem.7b00097.

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 Creators:
Suturina, Elizaveta A.1, 2, Author           
Nehrkorn, Joscha3, Author
Zadrozny, Joseph M.4, 5, Author
Liu, Junjie6, 7, Author
Atanasov, Mihail1, 8, Author           
Weyhermüller, Thomas1, Author           
Maganas, Dimitrios1, Author           
Hill, Stephen6, 9, Author
Schnegg, Alexander3, Author
Bill, Eckhard1, Author           
Long, Jeffrey R.4, Author
Neese, Frank1, Author           
Affiliations:
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              
3Berlin Joint EPR Lab, Institute for Nanospectroscopy, Helmholtz-Zentrum Berlin für Materialien und Energie, Kekuléstraße 5, 12489 Berlin, Germany, ou_persistent22              
4Department of Chemistry, University of California Berkeley, Berkeley, California 94720, United States, ou_persistent22              
5Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States, ou_persistent22              
6National High Magnetic Field Laboratory, Tallahassee, Florida 32310, United States, ou_persistent22              
7Department of Physics, Clarendon Laboratory, University of Oxford, Parks Road, Oxford OX1 3PU, United Kingdom, ou_persistent22              
8Bulgarian Academy of Sciences, Institute of General and Inorganic Chemistry, Akad. Georgi Bontchev Street 11, 1113 Sofia, Bulgaria, ou_persistent22              
9Department of Physics, Florida State University, Tallahassee, Florida 32306, United States, ou_persistent22              

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 Abstract: The magnetic properties of pseudotetrahedral Co(II) complexes spawned intense interest after (PPh4)2[Co(SPh)4] was shown to be the first mononuclear transition-metal complex displaying slow relaxation of the magnetization in the absence of a direct current magnetic field. However, there are differing reports on its fundamental magnetic spin Hamiltonian (SH) parameters, which arise from inherent experimental challenges in detecting large zero-field splittings. There are also remarkable changes in the SH parameters of [Co(SPh)4]2– upon structural variations, depending on the counterion and crystallization conditions. In this work, four complementary experimental techniques are utilized to unambiguously determine the SH parameters for two different salts of [Co(SPh)4]2–: (PPh4)2[Co(SPh)4] (1) and (NEt4)2[Co(SPh)4] (2). The characterization methods employed include multifield SQUID magnetometry, high-field/high-frequency electron paramagnetic resonance (HF-EPR), variable-field variable-temperature magnetic circular dichroism (VTVH-MCD), and frequency domain Fourier transform THz-EPR (FD-FT THz-EPR). Notably, the paramagnetic Co(II) complex [Co(SPh)4]2– shows strong axial magnetic anisotropy in 1, with D = −55(1) cm–1 and E/D = 0.00(3), but rhombic anisotropy is seen for 2, with D = +11(1) cm–1 and E/D = 0.18(3). Multireference ab initio CASSCF/NEVPT2 calculations enable interpretation of the remarkable variation of D and its dependence on the electronic structure and geometry.

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Language(s): eng - English
 Dates: 2017-01-122017-02-222017-03-06
 Publication Status: Published in print
 Pages: 17
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.7b00097
 Degree: -

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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 56 (5) Sequence Number: - Start / End Page: 3102 - 3118 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669