Supramolecular Heteropolyoxopalladate {Pd15} Cluster Host Encapsulating a {Pd2} Dinuclear Guest: [PdII2-{H16-nPdII15O10(PO4)10}]n-

Ahigh-nuclearity polyoxopalladate compound, [PdII2⊂{H7PdII15O10(PO4)10}]9 {PdII17}, comprising a {Pd15} host occupied by a {Pd2} guest and the parent pristine “empty” [H7PdII15O10(PVO4)10]13 {Pd15} cluster have both been prepared and characterized by single-crystal X-ray crystallography, 31P NMR, CSI-MS, and XPS. The encapsulated {Pd2} has a short PdII PdII distance within the {Pd15} host. Solution studies indicate that the empty host and filled guest complex are in equilibrium with each other, and UV titrations revealed a binding constant of ca. 103 for the guest PdII ions, with a binding stoichiometry of almost 2.

Programmable surface-architectures derived from hybrid polyoxometalate-based clusters

The exploration of the self-organization of a range of the polyoxometalate-based molecular structures reveals a diverse range of surface patterns and morphologies on solid substrates of technological interest, including methylated and hydroxylated silicon surfaces (namely, SiCH3 and SiOH). By exploiting the interplay between the intrinsic molecular properties and the surface chemistry as well as dynamic spatiotemporal phenomena (e.g., dewetting), we show that these systems can yield 0D, 2D, and 3D architectures via solution deposition at the solid surface, including nanodots, discs, lamellas, porous networks, and layer-by-layer assemblies. In general, we observed that layer-by-layer growth …

Polyoxometalates complex architectures in thin films by exploiting physical and chemical processes at surfaces

Physical Processes and Chemical Processes guiding polyoxomatalates self-structuring on surfaces