Aqueous Stability of Zirconium Clusters, Including the Zr(IV) Hexanuclear Hydrolysis Complex [ZrO(OH)(HO)], from Density Functional Theory.

Framework materials constitute a broad family of solids that range from zeolites and metal-organic frameworks (MOFs) to coordination polymers. The synthesis of such network structures typically rely on precursor molecular building blocks. As an example, the UiO-66 MOF series is constructed of hexanuclear [ZrO(OH)(CO)] cluster nodes and linear carboxylate linkers.

Butyltin Keggin Ion with a Rare Four-Coordinate Ca Center.

Alkyltin clusters are exploited in nanolithography for the fabrication of microelectronics. The alkyltin Keggin family is unique among Keggin clusters across the periodic table; its members appear to favor the lower-symmetry β and γ isomers rather than the highly symmetrical α and ε isomers. Therefore, the alkyltin Keggin family may provide important fundamental information about the formation and isomerization of Keggin clusters.

Alkyltin clusters: the less symmetric Keggin isomers.

The Keggin structure is prevalent in nature and synthesis, self-assembled from many metals across the periodic table as both isolated clusters and building blocks of condensed framework oxides. Here we present a one-step synthesis to obtain the sodium-centered butyltin Keggin ion in high yield and high purity, important for mechanistic nanolithography studies. Extensive solution characterization (small-angle X-ray scattering, 1H, 13C and 119Sn nuclear magnetic resonance, electrospray mass spectrometry) also confirms solutions contain only the Na-centered dodecamers.