TY  - DATA
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/123456789/4465
AB  - Additional EPR spectra and computational details. Cartesian coordinates of all structures reoriented in a standard way, as explained in the main text.
PB  - American Chemical Society (ACS)
T2  - Inorganic Chemistry
T1  - Supplementary information for: "Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation"
DO  - 10.1021/acs.inorgchem.5b02368.s001
ER  - 

@misc{
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 = "Additional EPR spectra and computational details. Cartesian coordinates of all structures reoriented in a standard way, as explained in the main text.",
publisher = "American Chemical Society (ACS)",
journal = "Inorganic Chemistry",
title = "Supplementary information for: "Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation"",
doi = "10.1021/acs.inorgchem.5b02368.s001"
}

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). Supplementary information for: "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)..
https://doi.org/10.1021/acs.inorgchem.5b02368.s001

Zlatar M, Gruden M, Vassilyeva OY, Buvaylo EA, Ponomarev AN, Zvyagin SA, Wosnitza J, Krzystek J, Garcia-Fernandez P, Duboc C. Supplementary information for: "Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation". in Inorganic Chemistry. 2016;.
doi:10.1021/acs.inorgchem.5b02368.s001 .

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, "Supplementary information for: "Origin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigation"" in Inorganic Chemistry (2016),
https://doi.org/10.1021/acs.inorgchem.5b02368.s001 . .

TY  - 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 . .