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Issue 20, 2010
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Theoretical magnetochemistry of dinuclear manganese complexes: broken symmetry density functional theory investigation on the influence of bridging motifs on structure and magnetism

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Abstract

A systematic study of the magnetic coupling in homovalent (III-III and IV-IV) and heterovalent (III-IV) manganese dimers as a function of the chemical identity and coordination mode of the bridging ligands is carried out with the aim of establishing a reference library of magnetostructural correlations. Emphasis is placed on rationalising the results through analysis of the superexchange pathways in terms of corresponding orbitals. Additionally, the influence of specific structural distortions on magnetic properties is explored. Consistent with chemical intuition and decades of experience, oxo bridges are shown to be efficient mediators of superexchange, primarily through π-type pathways, whereas the introduction of bridging carboxylates inhibits the magnetic coupling of the metal centres by introducing structural distortions in the core and by reducing the antiferromagnetic contribution to the exchange. Protonation of oxo bridges is shown to induce a predictably systematic reduction in the magnitude of antiferromagnetic coupling by switching off the dominant antiferromagnetic exchange pathways. In the case of weakly coupled dimers, this can even induce a reversal of the coupling from antiferromagnetic to ferromagnetic.

Graphical abstract: Theoretical magnetochemistry of dinuclear manganese complexes: broken symmetry density functional theory investigation on the influence of bridging motifs on structure and magnetism

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Article information


Submitted
19 Jan 2010
Accepted
07 Apr 2010
First published
23 Apr 2010

Dalton Trans., 2010,39, 4959-4967
Article type
Paper

Theoretical magnetochemistry of dinuclear manganese complexes: broken symmetry density functional theory investigation on the influence of bridging motifs on structure and magnetism

D. A. Pantazis, V. Krewald, M. Orio and F. Neese, Dalton Trans., 2010, 39, 4959
DOI: 10.1039/C001286F

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