The first example of a molecular cerium vanadium oxide photocatalyst is presented. A cerium vanadium oxide cluster, (nBu₄N)₂[(Ce(dmso)₃)₂V^IVV^V ₁₁O₃₃Cl] × 2DMSO (1), was obtained by bottom-up self-assembly. The compound exhibits high visible-light photooxidative activity towards indigo with quantum efficiencies >10%. Initial mechanistic studies of the photooxidation reaction are presented. The structure of compound 1 is based on chiral, C₂-symmetric cluster anions and both enantiomers are present in the crystal lattice. Retrosynthetic analysis suggests that chiral building blocks are spontaneously formed by symmetry breaking during self-assembly. The assembly of 1 based on the chiral building blocks is discussed conceptually. Consequences of this assembly mechanism for the development of chiral molecular catalysts and photocatalysts are described.

An anionic molecular cobalt vanadium oxide cluster, (n-Bu₄N)₃[Co(AcO)V₄O₁₂] and its use as anion binding site is reported. Cluster formation is controlled by an anion-dependent dynamic solution equilibrium. Reversible anion binding in solution leads to significant spectral changes, allowing the ratiometric optical detection of the anion concentration in situ, even under harsh thermal conditions (T = 90 °C). Comparative studies showed that the spectral response is dependent on the type of anion so that carboxylates, weakly coordinating anions and halides can be distinguished.

Three new uranyl tungstates, α-, β-Cs₂[(UO₂)₂(W₂O₉)], and Rb₆[(UO₂)₇(WO₅)₂(W₃O₁₃)O₂], have been obtained by high temperature solid state reactions. All three compounds display novel structure topologies: α- and β-Cs₂[(UO₂)₂(W₂O₉)] are based upon layers with a new topology that can be related to the uranophane topology; Rb₆[(UO₂)₇(WO₅)₂(W₃O₁₃)O₂] is a rare example of a non-molecular inorganic phase with layers containing oxo-tungstate trimers. The structural relationship between α- and β-Cs₂[(UO₂)₂(W₂O₉)] can be assigned to polytypism.

The instantaneous formation of mechanically stable cerium vanadium oxide gels starting from soluble polyoxovanadates is reported together with initial application studies. Upon addition of phosphoric acid to solutions containing a vanadium oxide source (e.g. (nBu₄N)₄[V₄O₁₂]) and Ce³⁺, instantaneous formation (reaction time <1 s) of a vanadium oxide gel is observed. The gel shows unique mechanical and thermal stabilities (up to ∼180 °C). High permeability of the gel is observed, allowing its use for long-term acid delivery into aqueous media or for the adsorption of organic aromatic dye pollutants from solution. A range of spectroscopy and electron microscopy techniques provide insight into the gel formation and the gel composition: an intertwined 3D matrix of nanowires (d ∼ 10 nm) containing cerium, vanadium oxide and phosphate is identified as an inorganic matrix which enables the formation of the mechanically stable gel.