The Role of Tetrahedral Building Blocks in Low-Dimensional Oxohalide Materials

Sammanfattning: The structural architecture found in low-dimensional materials can lead to a number of interesting physical properties including anisotropic conductivity, magnetic frustration and non-linear optical properties. There is no standard synthesis concept described thus far to apply when searching for new low-dimensional compounds, and therefore control on the design of the new materials is of great importance.This thesis describes the synthesis, crystal structure and characterization of some new transition metal oxohalide compounds containing p-elements having a stereochemically active lone-pair. First row transition metal cations have been used in combination with SeIV, SbIII and TeIV ions as lone-pair elements and Cl- and Br- as halide ions. The lone-pairs do not participate in covalent bonding and are responsible for an asymmetric one-sided coordination. Lone-pair elements in combination with halide ions have shown to be powerful structural spacers that can confine transition metal building blocks into low-dimensional arrangements. The halide ions and lone-pairs reside in non-bonded crystal volumes where they interact through weak van der Waals forces. The transition metal atoms are most often arranged to form sheets, chains or small clusters; most commonly layered compounds are formed.To further explore the chemical system and to separate the transition metal entities even more the possibility to include tetrahedral building blocks such as phosphate-, silicate-, sulphate- and vanadate building blocks into this class of compounds has been investigated. Tetrahedral building blocks are well known for their ability of segmenting structural arrangements by corner sharing, which often leads to the formation of open framework structures. The inclusion of tetrahedral building blocks led to the discovery of interesting structural features such as complex hydrogen bonding, formation of unusual solid solutions or faulted stacking of layers.Compounds for which phase pure material could be synthesized have been characterized in terms of their magnetic properties. Most compounds were found to have antiferromagnetic spin interactions and indications of magnetic frustration could be observed in some of them.