Synthesis of functional supramolecular architectures by dynamic covalent exchange and hierarchical host-guest assembly

Abstract

The work described in this thesis attempts to uncover the great potential of two unprecedented dynamic chemical systems. The first system involves largely overlooked and underexplored dynamic covalent exchange in amidines. The second system involves multicomponent host-guest assembly involving fullerene C60. The two chemical systems explored in this thesis are conceptually intertwined by exploiting host-guest complexation and dynamic covalent exchange to produce functional supramolecular architectures. We demonstrated that amidinium ions, which undergo reversible exchange with primary amines, can form host-guest complexes with crown ethers and eventually afford the simplest mechanically interlocked molecules – [2]rotaxanes. We also showed that a large metal-organic cage constructed by dynamic metal-ligand exchange can host a strongly associated supramolecular complex between fullerene C60 and [10]cycloparaphenylene and modulate the regiochemistry of fullerene bis-additions.