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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. We have synthesized and structurally characterized a new butyltin Keggin cluster with a tetrahedral Ca2+ center, fully formulated [(BuSn)12(CaO4)(OCH3)12(O)4(OH)8]2+ (β-CaSn12). The synthesis is a simple one-step process. Extensive solution characterization including electrospray ionization mass spectrometry, small-angle X-ray scattering, and multinuclear (1H, 13C, and 119Sn) nuclear magnetic resonance shows β-CaSn12 is essentially phase-pure and stable. This differs from the previously reported Na-centered analogues that always form a mixture of β and γ isomers, with facile interconversion. Therefore, this study has clarified prior confusion over complex spectroscopic and crystallographic characterization of the Na-centered analogues. Density functional theory calculations showed the following stability order: γ-CaSn12 < γ-NaSn12 < β-CaSn12 < β-NaSn12. The β analogue is always more stable than the γ analogue, consistent with experiment. Notable outcomes of this study include a rare tetrahedral Ca coordination, a Na-free alkyltin cluster (important for microelectronics manufacturing), and a better understanding of Keggin families built of different metal cations.

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 [Zr 6 O 4 (OH) 4 (CO 2 ) 12 ] cluster nodes and linear carboxylate linkers. Unfortunately, these Zr MOF cluster nodes cannot currently be manufactured in a sustainable way, motivating a search for "green" alternative synthesis methods. Stabilizing the hexanuclear Zr(IV) cluster (i.e., the hexamer, {Zr 6 12+ }) without the use of organic ligation would enable the use of environmentally friendly solvents such as water. The Zr(IV) tetranuclear cluster (i.e., the tetramer, {Zr 4 8+ }) can be stabilized in solution with or without organic ligands, yet the hexamer has yet to be synthesized without supporting ligands. The reasons why certain zirconium clusters are favored in aqueous solution over others are not well understood. This study reports the relative thermodynamic instability of the hypothetical hexamer {Zr 6 12+ } compared to the ubiquitous {Zr 4 8+ } tetramer. Density functional theory calculations were performed to obtain the hydrolysis Gibbs free energy of these species and used to construct Zr Pourbaix diagrams that illustrate the effects of electrochemical potential, pH, and Zr(IV) concentration. It was found that the aqueous {Zr 6 12+ } hexamer is ∼17.8 kcal/mol less stable than the aqueous {Zr 4 8+ } tetramer at pH = 0, V = 0, and [Zr(IV)] = 1 M, which is an energy difference on the order of counterion interactions. Electronic structure analyses were used to explore trends in the highest occupied molecular orbital-lowest unoccupied molecular orbital gap, frontier molecular orbitals, and electrostatic potential distribution of these clusters. The evidence suggests that the aqueous {Zr 6 12+ } hexamer may be promoted with more strategic syntheses incorporating minimal ligands and counterions.