Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation
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2016
Authors
Zlatar, MatijaGruden, Maja
Vassilyeva, Olga Yu
Buvaylo, Elena A.
Ponomarev, A. N.
Zvyagin, S. A.
Wosnitza, J.
Krzystek, J.
Garcia-Fernandez, Pablo
Duboc, Carole
Article (Published version)
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The aim of this work was to determine and understand the origin of the electronic properties of Mn-IV complexes, especially the zero-field splitting (ZFS), through a combined experimental and theoretical investigation on five well-characterized mononuclear octahedral Mn-IV compounds, with various coordination spheres (N-6, N3O3, N2O4 in both trans (trans-N2O4) and cis configurations (cis-N2O4) and O4S2). High-frequency and -field EPR (HFEPR) spectroscopy has been applied to determine the ZFS parameters of two of MnLtrans-N2O4 and Mn(LO4S)2 these compounds,. While at X-band EPR, the axial-component of the ZFS tensor, D, was estimated to be +0.47 cm(-1) for MnLO4S2, and a D-value of +2.289(5) cm(-1) was determined by HFEPR, which is the largest D-magnitude ever measured for a Mn-IV complex. A moderate D value of -0.997(6) cm(-1) has been found for MnLtrans-N2O4. Quantum chemical calculations based on two theoretical frameworks (the Density Functional Theory based on a coupled perturbed a...pproach (CP-DFT) and the hybrid Ligand-Field DFT (LF-DFT)) have been performed to define appropriate methodologies to calculate the ZFS tensor for Mn-IV centers, to predict the orientation of the magnetic axes with respect to the molecular ones, and to define and quantify the physical origin of the different contributions to the ZFS. Except in the case of MnLtrans-N2O4, the experimental and calculated D values are in good agreement, and the sign of D is well predicted, LF-DFT being more satisfactory than CP-DFT. The calculations performed on MnLcis-N2O4 are consistent with the orientation of the principal anisotropic axis determined by single-crystal EPR, validating the calculated ZFS tensor orientation. The different contributions to D were analyzed demonstrating that the d-d transitions mainly govern D in Mn-IV ion. However, a deep analysis evidences that many factors enter into the game, explaining why no obvious magnetostructural correlations can be drawn in this series of Mn-IV complexes.
Source:
Inorganic Chemistry, 2016, 55, 3, 1192-1201Publisher:
- American Chemical Society (ACS)
Funding / projects:
- Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-172035)
- COST Action ECOSTBio (Explicit Control Over Spin-States in Technology and Biochemistry) including a STSM grant [CM1305, COST-STSM-CM1305-25068]
- HLD at HZDR, member of the European Magnetic Field Laboratory (EMFL)
- French National Agency for Research [ANR-09-JCJC-0087]
- US Department of Energy
- State of Florida
- NSF [DMR 1157490]
- Ramon and Cajal fellowship [RYC-2013-12515]
- IR-RPE CNRS [3443]
- Deutsche Forschungsgemeinschaft (DFG, Germany)
- HLD
- Labex arcane [ANR-11-LABX-003]
Note:
- Supplementary information: https://cer.ihtm.bg.ac.rs/handle/123456789/4465
Related info:
- Referenced by
https://cer.ihtm.bg.ac.rs/handle/123456789/4465
DOI: 10.1021/acs.inorgchem.5b02368
ISSN: 0020-1669
PubMed: 26745448
WoS: 000369356800025
Scopus: 2-s2.0-84956707159
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IHTMTY - JOUR AU - Zlatar, Matija AU - Gruden, Maja AU - Vassilyeva, Olga Yu AU - Buvaylo, Elena A. AU - Ponomarev, A. N. AU - Zvyagin, S. A. AU - Wosnitza, J. AU - Krzystek, J. AU - Garcia-Fernandez, Pablo AU - Duboc, Carole PY - 2016 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1955 AB - The aim of this work was to determine and understand the origin of the electronic properties of Mn-IV complexes, especially the zero-field splitting (ZFS), through a combined experimental and theoretical investigation on five well-characterized mononuclear octahedral Mn-IV compounds, with various coordination spheres (N-6, N3O3, N2O4 in both trans (trans-N2O4) and cis configurations (cis-N2O4) and O4S2). High-frequency and -field EPR (HFEPR) spectroscopy has been applied to determine the ZFS parameters of two of MnLtrans-N2O4 and Mn(LO4S)2 these compounds,. While at X-band EPR, the axial-component of the ZFS tensor, D, was estimated to be +0.47 cm(-1) for MnLO4S2, and a D-value of +2.289(5) cm(-1) was determined by HFEPR, which is the largest D-magnitude ever measured for a Mn-IV complex. A moderate D value of -0.997(6) cm(-1) has been found for MnLtrans-N2O4. Quantum chemical calculations based on two theoretical frameworks (the Density Functional Theory based on a coupled perturbed approach (CP-DFT) and the hybrid Ligand-Field DFT (LF-DFT)) have been performed to define appropriate methodologies to calculate the ZFS tensor for Mn-IV centers, to predict the orientation of the magnetic axes with respect to the molecular ones, and to define and quantify the physical origin of the different contributions to the ZFS. Except in the case of MnLtrans-N2O4, the experimental and calculated D values are in good agreement, and the sign of D is well predicted, LF-DFT being more satisfactory than CP-DFT. The calculations performed on MnLcis-N2O4 are consistent with the orientation of the principal anisotropic axis determined by single-crystal EPR, validating the calculated ZFS tensor orientation. The different contributions to D were analyzed demonstrating that the d-d transitions mainly govern D in Mn-IV ion. However, a deep analysis evidences that many factors enter into the game, explaining why no obvious magnetostructural correlations can be drawn in this series of Mn-IV complexes. PB - American Chemical Society (ACS) T2 - Inorganic Chemistry T1 - Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation VL - 55 IS - 3 SP - 1192 EP - 1201 DO - 10.1021/acs.inorgchem.5b02368 ER -
@article{ author = "Zlatar, Matija and Gruden, Maja and Vassilyeva, Olga Yu and Buvaylo, Elena A. and Ponomarev, A. N. and Zvyagin, S. A. and Wosnitza, J. and Krzystek, J. and Garcia-Fernandez, Pablo and Duboc, Carole", year = "2016", abstract = "The aim of this work was to determine and understand the origin of the electronic properties of Mn-IV complexes, especially the zero-field splitting (ZFS), through a combined experimental and theoretical investigation on five well-characterized mononuclear octahedral Mn-IV compounds, with various coordination spheres (N-6, N3O3, N2O4 in both trans (trans-N2O4) and cis configurations (cis-N2O4) and O4S2). High-frequency and -field EPR (HFEPR) spectroscopy has been applied to determine the ZFS parameters of two of MnLtrans-N2O4 and Mn(LO4S)2 these compounds,. While at X-band EPR, the axial-component of the ZFS tensor, D, was estimated to be +0.47 cm(-1) for MnLO4S2, and a D-value of +2.289(5) cm(-1) was determined by HFEPR, which is the largest D-magnitude ever measured for a Mn-IV complex. A moderate D value of -0.997(6) cm(-1) has been found for MnLtrans-N2O4. Quantum chemical calculations based on two theoretical frameworks (the Density Functional Theory based on a coupled perturbed approach (CP-DFT) and the hybrid Ligand-Field DFT (LF-DFT)) have been performed to define appropriate methodologies to calculate the ZFS tensor for Mn-IV centers, to predict the orientation of the magnetic axes with respect to the molecular ones, and to define and quantify the physical origin of the different contributions to the ZFS. Except in the case of MnLtrans-N2O4, the experimental and calculated D values are in good agreement, and the sign of D is well predicted, LF-DFT being more satisfactory than CP-DFT. The calculations performed on MnLcis-N2O4 are consistent with the orientation of the principal anisotropic axis determined by single-crystal EPR, validating the calculated ZFS tensor orientation. The different contributions to D were analyzed demonstrating that the d-d transitions mainly govern D in Mn-IV ion. However, a deep analysis evidences that many factors enter into the game, explaining why no obvious magnetostructural correlations can be drawn in this series of Mn-IV complexes.", publisher = "American Chemical Society (ACS)", journal = "Inorganic Chemistry", title = "Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation", volume = "55", number = "3", pages = "1192-1201", doi = "10.1021/acs.inorgchem.5b02368" }
Zlatar, M., Gruden, M., Vassilyeva, O. Y., Buvaylo, E. A., Ponomarev, A. N., Zvyagin, S. A., Wosnitza, J., Krzystek, J., Garcia-Fernandez, P.,& Duboc, C.. (2016). Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation. in Inorganic Chemistry American Chemical Society (ACS)., 55(3), 1192-1201. https://doi.org/10.1021/acs.inorgchem.5b02368
Zlatar M, Gruden M, Vassilyeva OY, Buvaylo EA, Ponomarev AN, Zvyagin SA, Wosnitza J, Krzystek J, Garcia-Fernandez P, Duboc C. Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation. in Inorganic Chemistry. 2016;55(3):1192-1201. doi:10.1021/acs.inorgchem.5b02368 .
Zlatar, Matija, Gruden, Maja, Vassilyeva, Olga Yu, Buvaylo, Elena A., Ponomarev, A. N., Zvyagin, S. A., Wosnitza, J., Krzystek, J., Garcia-Fernandez, Pablo, Duboc, Carole, "Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation" in Inorganic Chemistry, 55, no. 3 (2016):1192-1201, https://doi.org/10.1021/acs.inorgchem.5b02368 . .