Title: Design of functional materials from molecular building blocks
Description: This dissertation is a summary of my research developing the synthesis and assembly of functional materials from nanoscale building blocks and studying their emergent properties. Chapter 1 introduces superatoms as exciting atomically precise supramolecular building blocks for materials design. Bottom-up assembly of these superatoms into materials with increased dimensionality (0D, 1D, 2D, and 3D) offers exciting opportunities to create novel solid-state compounds with tailored functions for widespread technological applications. I review recent advances to assemble superatomic materials and focus on assemblies from metal chalcogenide clusters and fullerenes. In subsequent chapters, I employ several of these nanoscale superatoms as the precursors to functional materials. Chapter 2 describes the synthesis and structural characterization of a hybrid solid-state compound assembled from two building blocks: a nickel telluride superatom and an endohedral fullerene. Although a varied library of binary superatomic solids has been assembled from fullerenes, this is the first demonstration of a superatomic assembly using an endohedral fullerene as a building block.

Lu3N@C80 fullerenes are dimerized in this new solid-state compound with an unpreceded orientation of the encapsulated metal nitride cluster. I explore the structural characterization of this material supported with computational evidence to explain the dimerization and orientation of the endohedral fullerenes. In Chapter 3 I begin to detail my exploration into assembling superatoms at micro and meso-scales –which will be the focus of Chapters 3-5. Polymers offer attractive mechanical and self-assembly properties that when combined with the attractive redox, optical, and magnetic properties of molecular clusters, these materials chart new paths to developing advanced materials and technologies. Chapter 3 describes charge transfer interactions between perylene diimide and cobalt telluride superatoms that drive the assembly of a solid-state compound from these two building blocks and inspired the design of a diblock copolymer template. Chapters 4 and 5 detail the synthesis and characterization of a polymer with functionalized cobalt selenide side units.

I describe a cationic homopolymer in Chapter 4 and diblock copolymer in Chapter 5 synthesized from ring opening polymerization of norbornene-derived monomers. Chapter 4 describes potential applications of the homopolymer system such as thin film fabrication. Chapter 5 discusses the self-assembly of the redox-active diblock copolymer into cross-linkable vesicle structures that can encapsulate molecular cargo. Finally, in Chapter 6 I introduce a new molecular building block to form gold metal surface bonds. Bisaminocyclopropenylidenes (BACs) are a class of carbenes that, much like N-heterocyclic carbenes, have been widely employed for catalysis but have yet to be explored for materials design. This chapter describes the structure and binding orientation of a BAC on an Au(111) surface. Each of these chapters illustrates how the synthetic flexibility of molecular building blocks enables the design of functional materials with tunable properties.