Quantitative Modelization of Hydrogen-Bonding in Polyoxometalate Chemistry

The PACHA (Partial Atomic Charges and Hardnesses Analysis) formalism is applied to polyoxometalate chemistry. Using the Ca₂(H₃O)₂[V₁₀O₂₈]16H₂O crystal structure, it was shown that the relative affinity for protons of the various oxygen sites may be quantitatively determined. The charge distribution was also found to be in good agreement with ¹⁷O and ⁵¹V NMR measurements. The H-bond energy in this kind of compound was found to be about –17 kJmol^–1, i.e., about 20% lower than in hexagonal ice. Finally, the 57 H-atom coordinates characterizing this structure were successfully recovered from a crystal structure optimization in the solid-state through electrostatic balance minimization. The importance of considering neutral clusters for a good modelization was demonstrated not only in the case of the decavanadate structure, but also in polysilicate chemistry. For the first time a clear picture emerges explaining the widespread occurrence of four- and five-membered rings in zeolite and silicate chemistry. The possibility of forming much larger polyanions with transition metal cations, is well explained using the crystal structure of the superfullerene keplerate [Mo₁₃₂O₃₇₂(HCO₂)₃₀(H₂O)₇₂]^42– as a benchmark compound. The possibility of performing an ab-initio retrosynthetic analysis of this cage is demonstrated.