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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, 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

Harvard

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

APA

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

Vancouver

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. doi: 10.1021/acs.inorgchem.7b00097

Author

Suturina, Elizaveta A. ; Nehrkorn, Joscha ; Zadrozny, Joseph M. 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. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 5. pp. 3102-3118.

BibTeX

@article{1accf45712b74958a97a5497a4ca0b1e,
title = "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",
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.",
keywords = "MAGNETIC CIRCULAR-DICHROISM, SINGLE-MOLECULE MAGNETS, PARAMAGNETIC-RESONANCE HFEPR, ZETA VALENCE QUALITY, GAUSSIAN-BASIS SETS, HIGH-FIELD EPR, ZERO-FIELD, HIGH-FREQUENCY, THEORETICAL-ANALYSIS, ATOMS LI",
author = "Suturina, {Elizaveta A.} and Joscha Nehrkorn and Zadrozny, {Joseph M.} and Junjie Liu and Mihail Atanasov and Thomas Weyherm{\"u}ller and Dimitrios Maganas and Stephen Hill and Alexander Schnegg and Eckhard Bill and Long, {Jeffrey R.} and Frank Neese",
year = "2017",
month = mar,
day = "6",
doi = "10.1021/acs.inorgchem.7b00097",
language = "English",
volume = "56",
pages = "3102--3118",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "5",

}

RIS

TY - JOUR

T1 - 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

AU - Suturina, Elizaveta A.

AU - Nehrkorn, Joscha

AU - Zadrozny, Joseph M.

AU - Liu, Junjie

AU - Atanasov, Mihail

AU - Weyhermüller, Thomas

AU - Maganas, Dimitrios

AU - Hill, Stephen

AU - Schnegg, Alexander

AU - Bill, Eckhard

AU - Long, Jeffrey R.

AU - Neese, Frank

PY - 2017/3/6

Y1 - 2017/3/6

N2 - 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.

AB - 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.

KW - MAGNETIC CIRCULAR-DICHROISM

KW - SINGLE-MOLECULE MAGNETS

KW - PARAMAGNETIC-RESONANCE HFEPR

KW - ZETA VALENCE QUALITY

KW - GAUSSIAN-BASIS SETS

KW - HIGH-FIELD EPR

KW - ZERO-FIELD

KW - HIGH-FREQUENCY

KW - THEORETICAL-ANALYSIS

KW - ATOMS LI

UR - http://www.scopus.com/inward/record.url?scp=85014542185&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.7b00097

DO - 10.1021/acs.inorgchem.7b00097

M3 - Article

C2 - 28225611

AN - SCOPUS:85014542185

VL - 56

SP - 3102

EP - 3118

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

ER -

ID: 10276888