In this review we summarise the quantum chemistry studies carried out by several groups over the last ten years on polyoxometalates, or polyoxoanions. This is an immense family of compounds made up of transition metal ions in their highest oxidation state and oxo ligands. The continuous progress of computers in general, and quantum chemistry software in particular, has enabled a number of topic...

Oxidation of the manganese-substituted polyoxometalate [SiW(11)Mn(II)(H(2)O)O(39)](6-) (SiW(11)Mn(II)) to [SiW(11)Mn(III)(H(2)O)O(39)](5-) (SiW(11)Mn(III)), one of the most selective polyoxometalates for the kraft pulp delignification, by versatile peroxidase (VP) was studied. First, SiW(11)Mn(II) was demonstrated to be quickly oxidized by VP at room temperature in the presence of H(2)O(2) (K(m...

[HIr(IV)W6O24](7-), representing the first Ir-containing Anderson-Evans-type polyanion and the first structurally characterized Ir(IV)-based polyoxometalate, has been isolated as its hydrated sodium salt and characterized by single-crystal X-ray diffraction, mass spectrometry, and IR, UV-Vis and EPR spectroscopy. Cyclic voltammetry indicates that the Ir(IV) ions in [HIrW6O24](7-) can undergo re...

Herein, the synthesis, characterization and photocatalytic application of a novel hybrid polyoxometalate, which can absorb light in the visible region, are reported. This hybrid material was synthesized by attaching a monovacant polyoxometalate, (SiW11O39), through a (3-aminopropyl)triethoxysilane linker to the anthracene. The hybridization with anthracene drastically decreased the band gap of ...

Inorganic-organic hybrid crystals were successfully obtained as single crystals by using polyoxotungstate anion and cationic dodecylpyridazinium (C12pda) and dodecylpyridinium (C12py) surfactants. The decatungstate (W10) anion was used as the inorganic component, and the crystal structures were compared. In the crystal comprising C12pda (C12pda-W10), the heterocyclic moiety directly interacted ...

The anti-DNA polymerase activity of a structural family of polyoxometalates has been determined. Two representative compounds of this family, possessing a saddle-like structure [(O3POPO3)4W12O36]16- (polyoxometalate I) and [(O3PCH2PO3)4W12O36]16- (polyoxometalate II) were found to inhibit all the DNA polymerases tested, with IC50 values ranging from 2 to 10 microM. A comparative study with HIV-...

Graphene oxide (GO) nanosheets and polyoxometalate such as H(3)PW(12)O(40) (PTA) are prepared into a multilayer film via a layer-by-layer inkjet printing method. The GO/PTA composite thin film shows linear, uniform and regular layer-by-layer growth. Under UV-irradiation, a photoreduction reaction takes place in the film which converts GO to reduced GO (rGO) due to the photoreduction activity of...

Inorganic-organic hybrid crystals containing α-octamolybdate (Mo8) or hexamolybdate (Mo6) were isolated by using hexadecyltrimethylammonium (C16) surfactant. The packing mode of the inorganic layers depended on a difference in the polyoxomolybdate molecular structure. The structure for both crystals consisted of alternate stacking of C16 organic bilayers and polyoxomolybdate inorganic layers wi...

We report examples of crystal surface modification of polyoxometalate open frameworks whereby the use of pyrrole or aniline as monomers leads to the formation of the corresponding polymers via an oxidative polymerization process initiated by the redox active POM scaffolds. Guest-exchange experiments demonstrate that the polymers can finely tune the guest exchange rate and their structural integ...