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http://hdl.handle.net/2445/154619
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DC Field | Value | Language |
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dc.contributor.author | Aravena, Daniel | - |
dc.contributor.author | Venegas-Yazigi, Diego | - |
dc.contributor.author | Ruiz Sabín, Eliseo | - |
dc.date.accessioned | 2020-04-01T08:24:18Z | - |
dc.date.available | 2020-04-01T08:24:18Z | - |
dc.date.issued | 2016-07-04 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | http://hdl.handle.net/2445/154619 | - |
dc.description.abstract | Single-molecule magnet (SMM) properties of transition-metal complexes coordinated to lacunary polyoxo-metalates (POM) are studied by means of state of the art ab initio methodology. Three [M(gamma-SiW10O36)(2)] (M =Mn-III Fe-III, Co-II) complexes synthesized by Sato et al. (Chem. Commun. 2015, 51, 4081-4084) are analyzed in detail. SMM properties for the Coll and Mninnsystems can be rationalized due to the presence of low-energy excitations in the case of Co-II, which are much higher in energy in the case of Mn-II. The magnetic behavior of both cases is consistent with simple d-orbital splitting considerations. The case of the Fe-III complex is special, as it presents a sizable demagnetization barrier for a high-spin d(5) configuration, which should be magnetically isotropic. We conclude that a plausible explanation for this behavior is related to the presence of low-lying quartet and doublet states from the iron(III) center. This scenario is supported by ab initio ligand field analysis based on complete active space self-consistent field results, which picture a d-orbital splitting that resembles more a square-planar geometry than an octahedral one, stabilizing lower multiplicity states. This coordination environment is sustained by the rigidity of the POM ligand, which imposes a longer axial bond distance to the inner oxygen atom in comparison to the more external, equatorial donor atoms. | - |
dc.format.extent | 9 p. | - |
dc.format.mimetype | application/pdf | - |
dc.language.iso | eng | - |
dc.publisher | American Chemical Society | - |
dc.relation.isformatof | Versió postprint del document publicat a: https://doi.org/10.1021/acs.inorgchem.6b00145 | - |
dc.relation.ispartof | Inorganic Chemistry, 2016, vol. 55, num. 13, p. 6405-6413 | - |
dc.relation.uri | https://doi.org/10.1021/acs.inorgchem.6b00145 | - |
dc.rights | (c) American Chemical Society , 2016 | - |
dc.source | Articles publicats en revistes (Química Inorgànica i Orgànica) | - |
dc.subject.classification | Anisotropia | - |
dc.subject.classification | Magnetisme | - |
dc.subject.other | Anisotropy | - |
dc.subject.other | Magnetism | - |
dc.title | Single-molecule magnet properties of transition-metal ions encapsulated in lacunary polyoxometalates: a theoretical study | - |
dc.type | info:eu-repo/semantics/article | - |
dc.type | info:eu-repo/semantics/acceptedVersion | - |
dc.identifier.idgrec | 666998 | - |
dc.date.updated | 2020-04-01T08:24:18Z | - |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | - |
Appears in Collections: | Articles publicats en revistes (Química Inorgànica i Orgànica) |
Files in This Item:
File | Description | Size | Format | |
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666998.pdf | 984.89 kB | Adobe PDF | View/Open |
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