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dc.creatorZlatar, Matija
dc.creatorGruden, Maja
dc.creatorVassilyeva, Olga Yu
dc.creatorBuvaylo, Elena A.
dc.creatorPonomarev, A. N.
dc.creatorZvyagin, S. A.
dc.creatorWosnitza, J.
dc.creatorKrzystek, J.
dc.creatorGarcia-Fernandez, Pablo
dc.creatorDuboc, Carole
dc.date.accessioned2019-01-30T17:50:27Z
dc.date.available2019-01-30T17:50:27Z
dc.date.issued2016
dc.identifier.issn0020-1669
dc.identifier.urihttp://cer.ihtm.bg.ac.rs/handle/123456789/1955
dc.description.abstractThe 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.en
dc.publisherAmer Chemical Soc, Washington
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172035/RS//
dc.relationCOST Action ECOSTBio (Explicit Control Over Spin-States in Technology and Biochemistry) including a STSM grant [CM1305, COST-STSM-CM1305-25068]
dc.relationHLD at HZDR, member of the European Magnetic Field Laboratory (EMFL)
dc.relationFrench National Agency for Research [ANR-09-JCJC-0087]
dc.relationUS Department of Energy
dc.relationState of Florida
dc.relationNSF [DMR 1157490]
dc.relationRamon and Cajal fellowship [RYC-2013-12515]
dc.relationIR-RPE CNRS [3443]
dc.relationDeutsche Forschungsgemeinschaft (DFG, Germany)
dc.relationHLD
dc.relationLabex arcane [ANR-11-LABX-003]
dc.rightsrestrictedAccess
dc.sourceInorganic Chemistry
dc.titleOrigin of the Zero-Field Splitting in Mononuclear Octahedral Mn-IV Complexes: A Combined Experimental and Theoretical Investigationen
dc.typearticle
dc.rights.licenseARR
dcterms.abstractГарциа-Фернандез, Пабло; Дубоц, Цароле; Груден, Маја; Вассилyева, Олга Yу; Буваyло, Елена A; Пономарев, A Н; Звyагин, С A; Крзyстек, Ј; Wоснитза, Ј; Златар, Матија;
dc.citation.volume55
dc.citation.issue3
dc.citation.spage1192
dc.citation.epage1201
dc.citation.other55(3): 1192-1201
dc.citation.rankaM21
dc.identifier.pmid26745448
dc.identifier.doi10.1021/acs.inorgchem.5b02368
dc.identifier.rcubConv_3484
dc.identifier.scopus2-s2.0-84956707159
dc.identifier.wos000369356800025
dc.type.versionpublishedVersion


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