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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

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Suturina,  Elizaveta A.
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;
Novosibirsk State University;

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Atanasov,  Mihail
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;
Bulgarian Academy of Sciences, Institute of General and Inorganic Chemistry;

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Weyhermüller,  Thomas
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Maganas,  Dimitrios
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Bill,  Eckhard
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

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.


Cite as: http://hdl.handle.net/21.11116/0000-0007-7950-7
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.