Crystalline polymers with well-defined structures have garnered considerable interest across multiple disciplines. Dynamic covalent chemistry (DCvC) is often employed in constructing crystalline polymers due to the light elements, covalent bonds, and error correction that facilitates the formation of ordered structures. Despite advancements, there remains a significant knowledge gap concerning the energetics of various polymeric phases and the impact of non-covalent interactions on the thermodynamics of the system. Recent progress in tuning the equilibrium has enabled the synthesis of high-quality crystalline samples for characterization with atomic resolution. Much of this progress has been centered on imine chemistry, leaving other DCvC linkages relatively unexplored. Charged borates present an avenue for creating intriguing and functionally relevant polymers. This thesis explores how dynamic borate chemistry can be utilized in crafting crystalline polymers. Additionally, this work explores the synergistic relationship between DCvC and supramolecular chemistry.

Chapter 1 will introduce Dynamic Covalent Chemistry and discuss state of the art for the synthesis of crystalline polymers. First, the fundamental principles of DCvC will be presented. Subsequently, recent progress in developing DCvC linkages and techniques for tuning their equilibrium will be discussed. Lastly, the design of topologies, polymetric phases, and the synergistic interplay between DCvC and supramolecular chemistry will be examined.

In Chapter 2, the discovery of a 3D COF as a metastable intermediate to the formation of a 1D helical covalent polymer (HCP) will be presented. The experimental evidence and theoretical calculation demonstrate that the 3D COF is a kinetically trapped state while the HCP topology is more thermodynamically favorable. This demonstrates that a series of hydrogen bonding interactions can be more favorable than a fully covalently bonded framework.

Chapter 3 will discuss new HCP structures developed by tuning the supramolecular interactions between the helical chains. The first portion will discuss the effect of counter-ion on the topology, which utilized single crystal XRD to unveil a novel entwinement mode. Then, ion exchange studies demonstrate that the hydrogen-bonded HCP can be converted into a metal-coordinated topology. In Chapter 4, I will present a novel borate linkage. By removing the chelating effect of the spiroborate, a novel tetra-substituted borate chemistry can be formed. This chapter will discuss frameworks synthesized by tetraborate and flexible linkages to form dia networks. Then, the utility of these materials will be demonstrated by their use in solid-state electrolytes for metal-ion batteries. Finally, Chapter 5 will review the previous chapters and suggest future works.