Syntheses and Applications of Boronate Ester-Capped Clathrochelate Complexes

This thesis describes the syntheses of novel boronate ester-capped clathrochelate complexes and their application in supramolecular chemistry, materials science, and chemical biology. Chapter 2 shows the synthesis of long Fe(II) dinuclear clathrochelates, up to 3 nm, with low synthetic effort. Their ability to be used as building blocks in supramolecular chemistry is evidenced by the formation of a Cu4L4-type coordination cage, and by the formation of a 2-dimensional metal-organic framework (MOF). The incorporation of clathrochelate complexes with terminal pyridyl groups into pillared MOFs by using solvent-assisted ligand exchange is described in Chapter 3. The strong basicity of clathrochelates with pyridyl groups makes them particularly suited for this approach. In Chapter 4, the structural characterization of novel cobalt clathrochelates is described. A first example of a Co(II) clathrochelate with potentially redox non-innocent phenanthrenequinone dioximato groups is reported. Chemical reductions of cobalt clathrochelates were carried out, and ligand effects are investigated by crystallography. Moreover, in the Chapter 5, clathrochelates with elongated π–dioximate groups are described, along with preliminary attempts of using them as three-way junction (TWJ) stabilizers. The synthesis of clathrochelate complexes with a chiral dioximato ligand and terminal pyridyl, bromo or carboxylic acid groups are described in Chapter 6. Potential applications of this new metalloligand in supramolecular chemistry are investigated.