Fluoride as Ligand: Chemistry of Some New Terminal and Bridged Systems

The thesis, “Fluoride as Ligand. Chemistry of some new Terminal and Bridged Systems” con sists of two parts. First part (Part I: Thesis), the proper thesis, consists of an introduction to the research area together with a description of a selection of results obtained during the project. Second part (Part II: Publications) is a complete collection of the scientific papers (Paper 1–10) at present time published or submitted to internationally recognized journals. These papers con stitute the formal yield of the project work. A comprehensive and unifying theme of the project, has been the synthesis and characterization of new coordination polymers and metalorganic networks, especially with focus on their magnetic properties. For all these systems, the common structural organizing element is the fluoride ion, which according to the Pearson classification is a “hard” or “class a” ligand. The properties of fluoride in general and in particular as ligand in coordination complexes is treated in Chapter 2. The fluoride ligand enters into unsupported bridging between a number of hard metals from both the main groups (sblock), transition metals periods (dblock) and lanthanoids (fblock). Chapter 3 summarizes some general aspects of magnetochemistry of relavance to the systems studied in the thesis work and the associated papers. A novel synthetic route to systems with unsuported, bridging fluorido ligands is established taking as employing kinetically robust Cr(III) fluorido complexes such as trans[Cr(py)4F2], cis [Cr(phen)2F2], cis[Cr(bpy)2F2] and cis[Cr(phen)2(H2O)(F)] as precursors. These metal containing building blocks (or ligands) can be viewed as synthons for the fluoride containing part of the final complex. The fluorido ligands in these robust synthons are fixed with respect to configuration, and due to the robustness of the synthons undesirable ligand substitution is