Supramolecular architectures with functionalised host ligands

This thesis concerns the rational design and controlled self-assembly of supramolecular architectures for application in areas such as molecular recognition. The research focuses on the cyclotriveratrylene family of molecular hosts, where their incorporation into both polyhedral and polymeric assemblies bestows hosting ability to the complexes isolated. A novel pyridine-N-oxide ligand library has been prepared and the first examples of formal coordination polymers of the lanthanide(III) cations are subsequently reported. Their self assembly was extended to the transition metals and a variety of coordination complexes were isolated that feature uncommon network topologies and structurally aesthetic motifs, such as large internal pore spaces. The combined effects of ligand solubility and rigidity were investigated and used to rationalise the selective isolation of a homochiral, triply-interlocked [2]-catenane over simple capsular assemblies. This was further exemplified in the isolation of a metastable cage complex which underwent a symmetry-induced inter-cage transformation to afford a much larger, polyhedral complex. The solution-phase chemistry of these cages was further investigated and a sophisticated assembly/disassembly cycle was determined. A stable family of cage complexes has been prepared using classical organometallic chemistry and self-assembly processes. Such cages were highly stable and their formation was observed to be cooperative. The solid state host-guest chemistry of these species was investigated, where they were observed to uptake various guests, including gaseous iodine, in a single-crystal-tosingle- crystal manner.