A thirty-year old mystery solved: identification of a new heptatungstate from non-aqueous solutions.

A new isopolyoxotungstate has been characterised, thirty years since the first spectroscopic evidence of its existence. The heptatungstate [WOH], containing a {W} lacunary Lindqvist unit fused to a ditungstate fragment, has significant stability and is only the third isopolytungstate structure to be obtained from non-aqueous systems.

Dynamics of encapsulated water inside Mo132 cavities.

The structure and dynamics of water confined inside a polyoxomolybdate molecular cluster [{(Mo)Mo(5)O(21)(H(2)O)(6)}(12){Mo(2)O(4)(SO(4))}(30)](72-) metal oxide nanocapsule have been studied by means of molecular dynamics simulations under ambient conditions. Our results are compared to experimental data and theoretical analyses done in reverse micelles, for several properties. We observe that the characteristic three-dimensional hydrogen bond network present in bulk water is distorted inside the cavity where water organizes instead in concentric layered structures.

Gated and differently functionalized (new) porous capsules direct encapsulates' structures: higher and lower density water.

By the deliberate choice of the internal ligands of the porous nanocapsules [{(Mo)Mo(5)}(12){Mo(2)(ligand)}(30)](n-), the respective cavities' shells can be differently sized/functionalized. This allows one to trap the same large number of water molecules, that is, 100 in a capsule cavity with formate ligands having a larger space available, as well as in a cavity containing sulfates and hypophosphites, that is, with less space. Whereas the 100 molecules fill the space completely in the second case in which they are organized in three shells, a four-shell system with underoccupation and broken hydrogen bonds is observed in the other case.

Keggin polyoxoanions in aqueous solution: ion pairing and its effect on dynamic properties by molecular dynamics simulations.

The dynamics of Keggin polyoxoanions in aqueous solution in the presence of monovalent cations is analyzed through molecular dynamics simulations. Together with structural information yielding the radial distribution functions of Li(+), Na(+), and K(+) with three polyoxometalates (POMs) bearing 3-, 4-, and 5- charges, the diffusion coefficient of these POMs is calculated. We found that the effect of the microscopic molecular details of the solvent is a key aspect to interpreting the structural and dynamic data because a competition between electrostatic interactions between the ions and the stability of the solvation shell is established.

DFT studies of uranyl acetate, carbonate, and malonate, complexes in solution.

The aim of this work is to demonstrate that theoretical chemistry can be used as a complementary tool in determining geometric parameters of a number of uranyl complexes in solution, which are not observable by experimental methods. In addition, we propose plausible structures with partial geometric data from experimental results. A gradient corrected DFT methodology with relativistic effects is used employing a COSMO solvation model.