Hetero-interpenetrated metal-organic frameworks : supramolecular interactions between ligands in metal-organic framework formation : a thesis presented in fulfilment of the requirements of the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatū, New Zealand

Metal-organic frameworks are an exciting class of materials formed through the self-assembly of their metal ion and organic ligand components into ordered, nanoporous lattice structures whose pore spaces are open to solvent, gas, and other guest molecules. Their consequently high surface areas render them suitable for diverse applications including gas storage, separations, and catalysis. The ability to precisely engineer the chemistry of the pores in framework materials and thus tune their properties is one of their most attractive features. Interpenetration, a phenomenon where multiple lattices are woven through each other, is an important handle on tuning their properties, mediating between pore shapes and volumes, chemistries, and robustness. In this thesis new frameworks are presented where two chemically distinct lattices are interpenetrated, a longstanding target in the field. These frameworks therefore have two orthogonal handles on both pore shape and functionalisation and have been applied to asymmetric organocatalysis by embedding an achiral catalytic site within a chiral pore space. Additionally, some insight is gained into the underlying principles of the formation of complex types of interpenetration through the exploitation of several analogous novel ligands