The development of new complex metal oxides having structural complexity suitable for solid-state catalysis is of great importance in fundamental catalysis research and practical applications. However, examples of these materials are rare. Herein, we report two types of crystalline complex metal oxides with new structures and their catalytic properties. The first one is an all-inorganic ε-Keggi...

The synthesis and molecular structure of a monomeric diplatinum(II) complex composed of mono-lacunary α-Keggin polyoxometalate is described. The polyoxometalate, Cs(3)[α-PW(11)O(39){cis-Pt(NH(3))(2)}(2)]·8H(2)O (Cs-1), afforded by a stoichiometric reaction of mono-lacunary Keggin polyoxotungstate with cis-diamminedichloroplatinum(ii) in water, followed by crystallization from water, was obtaine...

The asymmetric unit of the title compound, [Fe(C(8)H(7)N(3))(3)](2)[SiMo(14)O(44)], consists of a complex [Fe(C(8)H(7)N(3))(3)](2+) cation and half of a derivative of an α-Keggin-type anion, [SiMo(14)O(44)](4-). In the mixed-valent Mo(V/VI) anion, the α-Keggin type core is capped on two oppositely disposed tetra-gonal faces by additional (MoO(2)) units. The [SiMo(14)O(44)](4-) anion shows disor...

The structures and reactivity of fluoridated Keggin-aluminum tridecamers (K-Al13) in aqueous solution were studied using density functional theory (DFT) in order to explore the fluorine substitution process and the influence of F(-) on the chemical behavior of Keggin polynuclear Al species. The structures of fluoridated K-Al13 were optimized with the consideration of both explicit and bulk solv...

We present a quantitative evaluation of the influence of the electron transfer on the magnetic properties of mixed-valence polyoxometalates reduced by two electrons. For that purpose, we extract from valence-spectroscopy ab initio calculations on embedded fragments the value of the transfer integrals between W nearest-neighbor atoms in a mixed-valence alphaPW(12)O(40) polyoxowolframate Keggin a...

Two dysprosium-containing tungstoarsenates [C(NH(2))(3)](11)[Dy(2)(Hcit)(2)(AsW(10)O(38))]·9H(2)O (1) and K(8-n)H(3-n)[Dy(3-n)K(n)(H(2)O)(3)(CO(3))(A-α-AsW(9)O(34))(A-β-AsW(9)O(34))]·22H(2)O (n = 0 or 1) (2) have been synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, thermogravimetric analyses and infrared spectroscopy. Compound 1 is a citrate-decorated Kegg...

The encapsulation of three different cobalt substituted polyoxometalates (POMs) within the mesoporous chromium(iii) terephthalate MIL-101(Cr) metal-organic framework (MOF) was studied by a simple and green impregnation method using water. The POM@MIL composite materials were fully characterized by EDX, XRPD, IR, MAS NMR and N2 porosimetry measurements. The encapsulated POMs were then extracted ...

Catalytic and catalytic photo-assisted hydration of propene to form 2-propanol in gas-solid regime at atmospheric pressure and 85 °C were carried out by using a heteropolyacid (POM) supported on different oxides. Binary materials were prepared by impregnation of H3PW12O40 on different commercial and home prepared supports (TiO2, SiO2, WO3, ZrO2, ZnO, Al2O3). Some of the composites were active b...

Solid-state 13C NMR experiments and quantum chemical Density Functional Theory (DFT) calculations of acetone adsorption were used to study the location of protons in anhydrous 12-tungstophosphoric acid (HPW), the mobility of the isolated and hydrated acidic protons, and the acid strength heterogeneity of the anhydrous hydroxyl groups. This study presents the first direct NMR experimental eviden...