Molecular Containers Based on calix[4]pyrrole Scaffolds

This thesis comprises the synthesis and study of different molecular containers based on calix[4]pyrrole scaffolds. The molecular containers possess polar functionalized cavities ideal for the recognition of anions or N-oxides.  The preparation of containers with enforced cavities (cavitands) results in the formation of highly stable (both thermodynamic and kinetically) complexes. The conformations adopted in solution by the host and the solid-state geometry are discussed in detail. Furthermore, we also explore the host-guest chemistry of self-assembled molecular containers. We describe the formation of ordered co-encapsulation complexes of chloride with neutral guests within self-assembled hydrogen-bonded molecular capsules having a calix[4]pyrrole core. In a great synthetic effort, a bis[2]catenane molecular container was prepared by the mechanical link of a calixpyrrole and a calixarene hemisphere. The anisotropic cavity of the bis[2]catenane allowed for the co-encapsulation of small N-oxides along with a solvent molecule. The high kinetic stability of the host-guest complexes allowed for the stabilization of a reactive propargylic N-oxide. The observed kinetic stability was related to the thermodynamics of the host-guest complex by a kinetic model. Finally, we studied the synthesis and properties of covalent molecular containers. The preparation of carcerand-like compounds by the Hay coupling of a tetra-alkynyl calix[4]pyrrole afforded the unexpected formation of a figure-of-eight-like structure. The assembly of dynamic covalent capsules bearing reversible imine bonds was also explored using a tetra-aldehyde calix[4]pyrrole as scaffold. In both cases, it was found that the role of the template was vital in the efficient synthesis of the containers.