CHAPTER 8: Higher-order Supramolecular Systems Derived from Self-assembled Metallomacrocycles

Many examples from nature have demonstrated the power of hierarchical self-assembly in constructing structurally complex and functional architectures such as DNA and proteins. These examples, paired with the feasibility and efficiency of coordination-driven self-assembly, have led to significant studies on hierarchical self-assembly behaviours of self-assembled metallomacrocycles over the past few years. In this chapter, we summarize recent advances in the development of supramolecular structures and functional materials that contain metallomacrocycles as their main scaffold via hierarchical self-assembly. These systems have been classified based on the type of secondary driving force employed during the hierarchical self-assembly process. By changing the type of additional non-covalent interactions embodied in their building blocks, different functional materials, such as metallohydrogels, amphiphilic nanostructures, and stimuli-responsive supramolecular polymers, with tailored chemical and physical properties, have been prepared. Potential applications of these supramolecular systems are also briefly discussed.