The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond.

Catechols occupy a unique role in the structural, bio-, and geochemistry of silicon. Although a wealth of knowledge exists on their hypercoordinate complexes, the structure of tetracoordinate bis(catecholato)silane, Si(catH)2 1, has been enigmatic since its first report in 1951. Indeed, the claim of a planar-tetracoordinated silicon in 1 triggered a prominent debate, which is unsettled to this day. Herewith, we present a comprehensive structural study on 1 and derivatives in the gas phase by electron diffraction, in a neon matrix by IR spectroscopy, in solution by diffusion NMR spectroscopy, and in the solid-state by X-ray diffraction and MAS NMR spectroscopy, complemented by high-level quantum-chemical computations. The compound exhibits unprecedented phase adaptation. In the gas phase, the monomeric bis(catecholato)silane is tetrahedral, but in the condensed phase, it is metastable toward oligomerization up to a degree controllable by the type of catechol, temperature, and concentration. For the first time, spectroscopic evidence is obtained for a rapid Si-O σ-bond metathesis reaction. Hence, this study sorts out a long-lasting debate and confirms dynamic covalent features for our Earth's crust's most abundant chemical bond.

Structural variation, magnetism and single-source deposition of lanthanide-containing polyoxotitanates.

Heterometal-containing polyoxotitanates (POTs) are much-studied single-source precursors (SSPs) for doped TiO2. In this work the properties of a wide range of lanthanide-containing POTs are studied to assess their potential use as SSPs for Ln-Ti hybrid oxides. The novel cage compounds [{Ti2O(OEt)8}(EtOH·LnCl)]2 (Ln = Sm, Gd, Tb, Dy, Ho, Tm and Yb) are structurally characterised. The magnetic properties of the Ln = Dy and Ho compounds were characterised using SQUID magnetometry-in both cases, there is evidence of significant uniaxial magnetic anisotropy, but magnetic relaxation is fast and therefore no single-molecule magnetic properties are observed. Upon decomposition lanthanide-doped anatase (Ln = La) or titania/LnTi-oxide mixtures are obtained, which show efficient stabilisation of the catalytically active anatase phase up to high temperatures, making the materials of potential interest for applications in photocatalysis.

Titanium compounds containing naturally occurring dye molecules.

A range of titanium compounds containing the naturally occurring dyes quinizarin (QH2) and alizarin (AH2) was synthesized and structurally characterized in the solid state. Among these is the first examples of a discrete metallocyclic arrangement formed exclusively using quinizarin ligands and the first examples of lanthanide containing titanium compounds of the alizarin family of ligands.