UC Riverside

One of the ultimate goals within the field of supramolecular chemistry is to mimic the molecular recognition and catalytic activity of enzymes. Enzymes are more effective catalysts compared to human-made catalysts in terms of reaction specificity, rate of reaction, and capacity for substrate regulation, largely due to the characteristics (shape, size, electron density, functional groups) of the interior of the enzyme where the catalytic activity takes place. Supramolecular chemists can achieve this goal by creating assemblies with endohedral functionality that can mimic the interior cage-like nature of enzymes, mimic the asymmetric nature of enzyme active sites, and mimic the allosteric and cooperative nature of enzymes. This thesis takes steps towards achieving that goal by synthesizing and studying cages with endohedral functionality. Particularly, 1) self-assembled transition metal-ligand cages with (and without) endohedral functionality, 2) polyazacryptand cages with homo and hetero dinuclear metallation, and 3) allosterically regulated hydrogen bisulfate anion binding of a series of azacryptand ureas.