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

Elizaveta A. Suturina; Joscha Nehrkorn; Joseph M. Zadrozny; Junjie Liu; Mihail Atanasov; Thomas Weyhermüller; Dimitrios Maganas; Stephen Hill; Alexander Schnegg; Eckhard Bill; Jeffrey R. Long; Frank Neese

doi:10.1021/acs.inorgchem.7b00097

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

Elizaveta A. Suturina
, Joscha Nehrkorn
, Joseph M. Zadrozny
, Junjie Liu
, Mihail Atanasov
, Thomas Weyhermüller
, Dimitrios Maganas
, Stephen Hill
, Alexander Schnegg
, Eckhard Bill
, Jeffrey R. Long
, Frank Neese

Department of Chemistry

Max Planck Institute for Chemical Energy Conversion
Novosibirsk State University
Helmholtz Centre Berlin for Materials and Energy
University of California
Northwestern University
National High Magnetic Field Laboratory
University of Oxford
Bulgarian Academy of Sciences
Florida State University

Research output: Contribution to journal › Article › peer-review

99 Citations (SciVal)

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.

Original language	English
Pages (from-to)	3102-3118
Number of pages	17
Journal	Inorganic Chemistry
Volume	56
Issue number	5
Early online date	22 Feb 2017
DOIs	https://doi.org/10.1021/acs.inorgchem.7b00097
Publication status	Published - 6 Mar 2017

Funding

S.H. and J.R.L. acknowledge support from the the U.S. National Science Foundation under Grant Nos. DMR-1309463, DMR- 1610226, and CHE-1464841. Work performed at the National High Magnetic Field Laboratory is supported by the U.S. National Science Foundation through cooperative agreement No. DMR-1157490 and the State of Florida. E.A.S. acknowledges the Russian Science Foundation for support of the quantum chemical part of the work (project 16-13-10155). FDFT THz-EPR experiments were supported by the Deutsche Forschungsgemeinschaft (DFG) through priority program SPP 1601 and the BESSY II user program.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/acs.inorgchem.7b00097

Cite this

Suturina, E. A., Nehrkorn, J., Zadrozny, J. M., Liu, J., Atanasov, M., Weyhermüller, T., Maganas, D., Hill, S., Schnegg, A., Bill, E., Long, J. R., & Neese, F. (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. https://doi.org/10.1021/acs.inorgchem.7b00097

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, Elizaveta A.; Nehrkorn, Joscha; Zadrozny, Joseph M. et al.
In: Inorganic Chemistry, Vol. 56, No. 5, 06.03.2017, p. 3102-3118.

Research output: Contribution to journal › Article › peer-review

Suturina, EA, Nehrkorn, J, Zadrozny, JM, Liu, J, Atanasov, M, Weyhermüller, T, Maganas, D, Hill, S, Schnegg, A, Bill, E, Long, JR & Neese, F 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, vol. 56, no. 5, pp. 3102-3118. https://doi.org/10.1021/acs.inorgchem.7b00097

Suturina EA, Nehrkorn J, Zadrozny JM, Liu J, Atanasov M, Weyhermüller T et al. 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. 2017 Mar 6;56(5):3102-3118. Epub 2017 Feb 22. doi: 10.1021/acs.inorgchem.7b00097

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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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AU - Atanasov, Mihail

AU - Weyhermüller, Thomas

AU - Maganas, Dimitrios

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