A density functional theory study of the magnetic exchange coupling in dinuclear manganese(II) inverse crown structures.

Abstract

The magnetic exchange coupling constants between two Mn(II) centers for a set of five inverse crown structures have been investigated by means of a methodology based on broken-symmetry unrestricted density functional theory. These novel and highly unstable compounds present superexchange interactions between two Mn centers, each one with S = 5/2 through anionic "guests" such as oxygen, benzene, or hydrides or through the cationic ring formed by amide ligands and alkali metals (Na, Li). Magnetic exchange couplings calculated at B3LYP/6-31G(d,p) level yield strong antiferromagnetic couplings for compounds linked via an oxygen atom or hydride and very small antiferromagnetic couplings for those linked via a benzene molecule, deprotonated in either 1,4- or 1,3- positions. Analysis of the magnetic orbitals and spin polarization maps provide an understanding of the exchange mechanism between the Mn centers. The dependence of J with respect to 10 different density functional theory potentials employed and the basis set has been analyzed.

DOI: 10.1021/jp907200u

Cite this paper

@article{Vlez2009ADF, title={A density functional theory study of the magnetic exchange coupling in dinuclear manganese(II) inverse crown structures.}, author={Ederley V{\'e}lez and Antonio Alberola and V{\'i}ctor Polo}, journal={The journal of physical chemistry. A}, year={2009}, volume={113 50}, pages={14008-13} }