Density functional theory is used to investigate the structure and energetics of the tetrachloroplatinate anion and its hydrolysis products at several degrees of hydration, as well as those of outer dendrimer pockets hosting such species. The number of water molecules able to saturate an unprotonated outer dendrimer pocket is found to be two, as inferred from calculated thermodynamic data. However, such a number could not be established for a protonated pocket where the dendrimer adopts a more open configuration. An analysis of possible pocket configurations is done on the basis of the orientations of the amide O atoms in the outer pockets. The effect of explicit water on the infrared spectra of the dendrimer pockets is reported and compared to experimental values. © 2007 American Chemical Society.