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2016-07-04

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Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/154619

Single-molecule magnet properties of transition-metal ions encapsulated in lacunary polyoxometalates: a theoretical study

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https://doi.org/10.1021/acs.inorgchem.6b00145

Resum

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.

Matèries

Anisotropia, Magnetisme

Matèries (anglès)

Anisotropy, Magnetism

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Articles publicats en revistes (Química Inorgànica i Orgànica)

Citació

ARAVENA PONCE, Daniel Alejandro, VENEGAS-YAZIGI, Diego and RUIZ SABÍN, Eliseo. Single-molecule magnet properties of transition-metal ions encapsulated in lacunary polyoxometalates: a theoretical study. Inorganic Chemistry. 2016. Vol. 55, num. 13, pags. 6405-6413. ISSN 0020-1669. [consulted: 16 of August of 2026]. Available at: https://hdl.handle.net/2445/154619

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