Title: The Development of Functionally Tunable Hierarchical Nanomaterials
Description: Superatomic crystals (SACs) with tunable physical properties offer a new approach to the design of inorganic nanomaterials. Very little is known about how these systems function, or how their properties can be transformed. Here I describe work that helps to develop an understanding of how functional properties behave in SACs, and how they can be altered through superatomic intercalation or with phase transitions. Chapter 1 describes work characterizing the thermal transport behavior of SACs. We find that heat transfer is dominated by coherent inter-cluster phonons with vibrational frequencies determined by the periodicity of the SAC superstructure. We also demonstrate a transformation from amorphous to crystalline thermal transport behavior through manipulation of the vibrational landscape and orientational order of the superatoms. Chapters 2 and 3 describe the intercalation of a porous superatomic host, [Co₆Te₈(PⁿPr₃)₆][C₆₀]₃. We find that guests can be inserted into the superstructure through single-crystal-to-single-crystal transformations, dramatically transforming the electronic properties of the SAC.

Using electronic absorption spectroscopy, electrical transport measurements and electronic structure calculations, we demonstrate that the intercalation is driven by the exchange of charge between the host, establishing an exciting design space for the preparation of superatomic materials. Chapter 4 describes a hierarchical solid, [Co₆Te₈(PEt₃)₆][C₇₀]₂, in which the delicate balance of interactions between constituent building blocks produces two separate phase transitions: one affecting thermal transport properties, the other transforming the electronic and magnetic behavior of the SAC. We use a wide range of structural and spectroscopic characterization tools to understand the mechanism of each transformation. This work establishes a new ability to program functional phase transitions into cluster-assembled materials. In a completely different area of study, chapter 5 describes a new covalent organic framework (COF) whose unique structure enables a post-synthetic topochemical polymerization of the framework’s linker fragments.

The polymerization of the 1-3 butadiyne into a polydiacetylene backbone covalently crosslinks the material without compromising its original crystallinity. This work not only enables the preparation of more structurally resilient COFs, but also diversifies the design space for this emerging class of materials.