Base Catalysis of Sodium Salts of [Ta6−xNbxO19]8− Mixed-Oxide Clusters

The solid base catalysis of sodium salts of Lindqvist-type metal oxide clusters was investigated using a Knoevenagel condensation reaction. We successfully synthesized the sodium salts of Ta and Nb mixed-oxide clusters Na8−nHn[(Ta6−xNbx)O19]·15H2O (Na-Ta6−xNbx, n = 0, 1, x = 0–6) and found them to exhibit activity for proton abstraction from nitrile substrates with a pKa value of 23.8, which is comparable to that of the conventional solid base MgO. The Ta-rich Na-Ta6 and Na-Ta4Nb2 exhibited high activity among Ta and Nb mixed-oxide clusters. Synchrotron X-ray diffraction (SXRD) measurements, Fourier-transform infrared (FT-IR) spectroscopy, and X-ray absorption spectroscopy (XAS) revealed the structure of Na-Ta6−xNbx: (1) The crystal structure changed from Na7H[M6O19]·15H2O to Na8[M6O19]·15H2O (M = Ta or Nb) by the anisotropic expansion of the unit cell with an increase in Ta content; (2) Highly symmetrical Lindqvist [Ta6−xNbxO19]8− was generated in Na-Ta4Nb2 and Na-Ta6 because of the symmetrical association of Na+ ions with [Ta6−xNbxO19]8− in the structure. DFT calculation revealed that the Lindqvist structures with high symmetry have large NBO charges on surface oxygen species, which are strongly related to base catalytic activity, whereas the composition hardly affects the NBO charges. The above results showed that the Brønsted base catalysis was sensitive to the symmetry of the Lindqvist [Ta6−xNbxO19]8− structure. These findings contribute to the design of solid base catalysts composed of anionic metal oxide clusters with alkaline-metal cations.

The Ionization Energies of Dust-Forming Metal Oxide Clusters

Stellar dust grains are predominantly composed of mineralic, anorganic material forming in the circumstellar envelopes of oxygen-rich AGB stars. However, the initial stage of the dust synthesis, or its nucleation, is not well understood. In particular, the chemical nature of the nucleating species, represented by molecular clusters, is uncertain. We investigated the vertical and adiabatic ionization energies of four different metal-oxide clusters by means of density functional theory. They included clusters of magnesia (MgO)n, silicon monoxide (SiO)n, alumina (Al2O3)n, and titania (TiO2)n with stoichiometric sizes of n = 1–8. The magnesia, alumina, and titania clusters showed relatively little variation in their ionization energies with respect to the cluster size n: 7.1–8.2 eV for (MgO)n, from 8.9–10.0 eV for (Al2O3)n, and 9.3–10.5 eV for (TiO2)n. In contrast, the (SiO)n ionization energies decrease with size n, starting from 11.5 eV for n = 1, and decreasing to 6.6 eV for n = 8. Therefore, we set constraints on the stability limit for neutral metal-oxide clusters to persist ionization through radiation or high temperatures and for the nucleation to proceed via neutral–neutral reactions.

Constructing chiral polyoxometalate assemblies via supramolecular approaches

Polyoxometalates (POMs) as a typical class of discrete metal oxide clusters that are known in inorganic and structural chemistry for a long-term display more and more interesting applications over recent...