Dolores Melgar Freire, PhD student under the supervision of Prof. Carles Bo and Prof. Josep Bonet, has defended her PhD Thesis entitled “Keplerates: from Electronic Structure to Dynamic Properties” (assigned to the department of Chemical Engineering of the Universitat Rovira i Virgili) publicly on December 4th at the ICIQ Library.
The member of her evaluation committee were: Prof. Josep M. Poblet (Unviersitat Rovira i Virgili), Prof. Sébastien Floquet (Unviersité Versailles-Saint Quentin) and Prof. Fernando Bresme (Imperial College London).
This Thesis is focused on the study of Keplerates: a family of sizable polyoxometalates (POM) with icosahedral symmetry. POMs are anionic inorganic clusters composed of MOn units. M represents a transition metal atom usually in its highest state of oxidation (MoVI, WVI, VV, etc.). One of the most representative examples of Keplerates is the Mo132capsule, namely [(MoVI5(MoVI)O21)12(MoV2O2(µ-O)2(Ln-)30](12+n)-, where L represents a bidentate ligands that decorates the inner surface of the Keplerate. Throughout this Thesis, the electronic structure of Keplerates has been studied at the Density Functional Theory (DFT) level. Furthermore, the interaction between the Mo132 capsule and its corresponding internal ligands has been studied by means of the same methodology. On the other hand, in collaboration with other groups, both theoretical and experimental, a formation mechanism of the Mo132 capsule has been proposed. Finally, a force field partially extracted from the previous DFT calculations has been applied to perform classical Molecular Dynamics simulations in order to study the behavior of the Mo132 macro-ion in aqueous solution, in the presence of different counter-cations species and at different temperatures. Particularly, the effect that the hydrophobic character of the counter-cations has on the plugging process of the Mo132 capsule has been analyzed.