Molecular Cages of Controlled Size and Shape
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
This thesis details the synthesis and coordination chemistry of twenty-five nitrogencontaining heterocyclic ligands, nineteen of which were previously unreported compounds. These ligands were designed for use as synthons for the formation of molecular cages, so contain multiple coordination sites capable of bridging multiple metal atoms. The majority of molecular cages in the literature are formed by rigid bridging ligands, whereas the ligands studied in this research incorporate a higher level of flexibility, thereby lessening the degree of control over the self-assembly process and increasing the number of possible structures that can be formed upon reaction of these ligands with meal salts. Three of the new ligands synthesised were two-armed bridging ligands, which were reacted with a wide variety of metal salts to investigate what self-assembly products were formed. The complexes characterised include a M₃L₃ cyclic trimer, a range of coordination polymers of varying dimensionality, a range of dimeric products and a series of M₄L₆ cage-like molecular squares. However, the majority of ligands studied were three-armed, potentially tripodal compounds, which were envisaged as potential components of M₃L₂ or M₆L₄ molecular cages. The products of self-assembly of these ligands with various metals salts were shown to include a variety of discrete tri- and tetranuclear complexes, a range of coordination polymers of varying dimensionality and interpenetration, and a complex M₆L₄ assembly that appears to be a collapsed coordination cage. Unfortunately some of the ligands synthesised were shown to decompose in the presence of various metal salts, a phenomenon already identified in the literature. Analogues of these decomposition products were synthesised deliberately to identify the potential of a known tridentate ligand as a metallosupramolecular synthon. ¹H NMR spectroscopy, mass spectrometry, elemental analysis, thermogravimetric analysis and X-ray crystallography were used to study the compounds synthesised. The crystal structures of five ligands and fifty-one complexes are discussed.