Lacunary polyoxometalates (POMs) are negatively charged metal–oxo clusters, formally obtained from plenary topologies via fragment removal. Owing to the removal, lacunary POMs archetypes rich in nucleophilic terminal oxo ligands, making them suitable for post-synthetic coordination with various heterometals. Trilacunary heteropolytungstates (hetero-POTs) based on bowl-shaped {W9O30} framework i...

Reaction products of titanium(IV) sulfate in HCl-acidic aqueous solution with the dimeric species linked through three intermolecular Ti-O-Ti bonds of the two trititanium(IV)-substituted α-Keggin polyoxometalate (POM) subunits are described. Two novel titanium(IV)-containing α-Keggin POMs were obtained under different conditions. One product was a dimeric species through two intermolecular Ti-O...

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEIs) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and application of solid-state in situ thin-film electrochemical cells to explore redox and catalytic processes occurring at well-defined EEIs gene...

A new amphiphilic molecule bearing poly(ethylene oxide) (PEO) and quaternary ammonium group, was designed and synthesized to encapsulate paramagnetic Gd(III)-containing polyoxometalate (Gd-POM) through electrostatic interaction for obtaining a water-soluble organic-inorganic hybrid building block based on POM. The yielding organic cation-encapsulated Gd-POM (OCEP-Gd) complex exhibited water-sol...

We describe how supramolecular assembly, mediated by control of the ratio of the hetero-atoms in the units [Mo2S2O2] 2+ and SeO3 2 leads to the formation of new types of building blocks, [(Mo2O2S2)3(OH)4(H2O)6(SeO3)] 1⁄4 {Mo6} and [(Mo2O2S2)2(OH)2(H2O)4(SeO3)] 1⁄4 {Mo4} which are linked in an type of inorganic ‘panelling’ to the assembly of a range of new clusters 1–3 with the general formula {...

The effect of acetate concentration on the formation of {SiW10Fe2}-based complexes is demonstrated by the synthesis of an open-shell diiron tungstosilicate derivative featuring two rotational Keggin isomer units.

A simple and facile one-step method for the synthesis of an organic dye-functionalized polyoxometalate (POM) hybrid with visible-light photo-response was reported. The POM hybrid was fully characterized via single crystal XRD, powder XRD, FTIR and elemental analysis. The reaction of the organic dye with inorganic salts gave the dye-functionalized POM (MoBB3), in which the POM cluster was formed...

Chemical transformations are normally conducted in batch or flow mode, thereby allowing the chemistry to be temporally or spatially controlled, but these approaches are not normally combined dynamically. However, the investigation of the underlying chemistry masked by the self-assembly processes that often occur in one-pot reactions and exploitation of the potential of complex chemical systems ...

A novel pyrene covalently-attached polyoxometalate (POM) hybrid has been synthesized and fully characterized. The attractive electronic and photophysical properties of pyrene derivatives make the hybrid promising for studying and understanding electron transfer mechanisms in organic-functionalized POMs. The hybrid has an electronic absorption at 450 nm, indicating that there is a strong electro...