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A morphological phase diagram is determined to relate the effect of base concentration and temperature during the hydrothermal synthesis with the final ceria nanostructured morphology. Representative samples of nanoparticles, nanorods and nanocubes have been characterised by XRD, N 2 adsorption, TEM, XPS and Raman and catalytically tested for the total oxidation of naphthalene as a model polycyclic aromatic hydrocarbon. Ceria nanoparticles present the highest surface area and smallest crystalline size, leading to the most active of these structures. However if the catalytic activity is normalized by unit of surface area, the observed reactivity trend (nanorods < nanocubes < nanoparticles) is directly related to the concentration of surface oxygen vacancies as a result of the exposure of the (110) and (100) preferential planes.

We report here a synthetic route to bis(N,N'-aryl)-6-aminofulvene-2-aldimine (AFA) ligand systems, specifically Ph(2)-AFAH and Dip(2)-AFAH. The synthesis and structural characterization of a series of Cu(I) complexes [(Ph(2)-AFA)Cu(CNPh)(2)] (2), [(Ph(2)-AFA)Cu(CN(i)Pr)] (3), and [(Dip(2)-AFA)Cu(CN(i)Pr)] (4), from the reaction of the corresponding lithiated AFA systems with Cu-Cl derivatives are reported; notably in the case of [(Ph(2)-AFA)Cu(CNPh)(2)] studies have revealed the existence of two structural isomers (2a and 2b), both of which can be isolated and structurally characterized. Density functional theory (DFT) calculations suggest that the two crystal forms are comparatively close in energy, and geometry optimization reveals a convergence of these two forms to a geometry that more closely resembles the solid-state structure of isomer 2b, having a CH···π interaction. The reactions of the AFA compounds Ph(2)-AFAH and Dip(2)-AFAH with ZnMe(2) and AlMe(3) have also been investigated, and the results of these reactions are described here.