Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
This thesis describes the preparation and characterisation of a number of metallosupramolecular assemblies. Such species were constructed by the reaction of ligands based on nitrogen containing heterocycles with metal atoms. The coordinate bonds used to hold these species together provide a mixture of strength and lability that aids the formation of interesting structures. The twenty six ligands utilised for the formation of metallosupramolecular species can be divided into three types; rigid sym-biheterocycles, ligands with added flexibility, and chiral ligands for the formation of polymers. These investigations used a range of metal atoms to allow the examination of the metallosupramolecular chemistry of these ligands. The structure of forty three complexes was determined using single crystal X-ray crystallography. The complexes isolated and characterised had a diverse range of structures, with discrete and polymeric species formed. The rigid sym-biheterocycles gave mostly monomeric and oligomeric complexes, with two polymeric complexes also formed; all ligands failed to coordinate through all donor atoms. Ligands with added flexibility gave mostly one- and two- dimensional polymers, with discrete complexes such as M2L2 macrocycles and mononuclear structures also formed. The chiral ligands prepared using camphor gave a range of clural polymers, and in two cases these possessed directionality. The variety of metallosupramolecular assemblies synthesised exemplifies the structural complexity that may be formed using metal atoms and N-heterocyclic ligands as structural components for molecular construction.