Role of the electron transfer and magnetic exchange interactions in the magnetic properties of mixed-valence polyoxovanadate complexes.

Modeling the properties of high-nuclearity, high-electron-population, mixed-valence (MV) magnetic systems remains one of the open challenges in molecular magnetism. In this work, we analyze the magnetic properties of a series of polyoxovananadate clusters of formula [V 18O 42] (12-) and [V 18O 42] (4-). The first compound is a fully localized spin cluster that contains 18 unpaired electrons located at the metal sites, while the second one is a MV cluster with 10 unpaired electrons largely delocalized over the 18 metal sites. A theoretical model that takes into account the interplay between electron transfer and magnetic exchange interactions is developed to explain the unexpected enhancement of the antiferromagnetic coupling when the number of unpaired electrons is reduced from 18 to 10 in these clusters. In the MV area, these systems represent the most complex magnetic clusters studied theoretically so far. Because of the high complexity of the systems, the number of relevant parameters is too large for a conventional model Hamiltonian approach. We therefore perform a theoretical study that combines ab initio calculations with the model Hamiltonian. In this way, we use ab initio calculations performed on small fragments of the cluster to lower the degrees of freedom of the parameter set of the model Hamiltonian that operates in the whole MV cluster. This approach shows the usefulness of combining ab initio calculations with model Hamiltonians in order to explore the magnetic properties of large and complex molecular systems, emphasizing the key role played by the electron transfer in these model magnetic materials.