Modern day industrial byproducts can produce many types of waste in the solid, liquid or gas form. Oxoanions is of particular concern due to high water solubility and persistent nature. Byproducts like perchlorate (ClO4–), chromate (CrO42–), and pertechnetate (TcO4–) are very toxic to the environment and must be disposed of properly. Often oxoanions are disposed of in aqueous form increasing the total amount of waste. To reduce total waste volume and clean natural water is through a form of sequestration essentially converting a toxic liquid into a condensed solid. Sequestration also allows for easy disposal as well as potential repurposing. Typical methods of anion sequestration involve some form of filter through a process of ion exchange effectively substituting the toxic ion for a non-toxic alternative. However, current technologies are limited by ion selectivity, capacity and cost. Wastewater can vary greatly by composition, concentration, pH and general reactivity. Metal-organic coordination polymers (CPs) have the potential to counter many of these limitations through their highly modular nature allowing for application engineering.xiii Chapter 1 focuses on methods of studying anion exchange CPs. Designing new CPs for anion exchange processing remains relatively slow due to a limited understanding of their fundamental driving forces, which hinders design for specific applications. Current methods of CP design often fall in a trial-and-error method. To improve the rate of success detailed understanding is necessary. With the help of computer simulations such as density functional theory can greatly benefit CP design. However, many limitations are still present as CPs are a unique material with strongly bound and weakly bound regions. Weakly bound periodic systems, materials typically with high van der Waals forces such as graphite are poorly modeled compared to strongly bound systems such as metal oxides. Therefore, it is essential for more rigorous computational studies specifically tailored to CPs to be performed. Chapter 2 focuses on combining experimental and theoretical work by performing detailed examinations between systems to help elucidate underlying forces. Silver bipyridyl cationic CPs have been shown to anion exchange extremely well and serve as a great reference material set. Through minor ligand modifications, computational studies and experimental thermodynamics have shown ligand-ligand interactions greatly stabilize the CP and sequestered anions. By comparing ligand energetic states, the process of crystallization has been shown to prefer flatter ligands. The ligand torsion applied through crystallization on silver 4,4′-bipyridne costs as much as 4.6 kJ/mol compared to 4,4′-vinylenedipyridine. This finding suggests ideal ligands crystallize in their energetically preferred state resulting in increased overall CP stability. Chapter 3 explores extensive computational of silver bipyridyl CPs. The anion exchange thermodynamics of silver bipyridyl CPs have proven to be difficult to accurately xiv model. During the anion exchange process vast changes in structure, volume and molecular composition occur. Modeling the enthalpy of formation compared to experimental Gibbs free energy of formation reveals that entropic factors can play a determining role, making simple predictions difficult. However, through the analysis of charge density of the computational relaxed structures localized interactions can be revealed. The CP formation is a redox reaction where the anion and cation gain electron density through the ligand and sometimes occluded solvent molecules. Specifically, ligand charge donation appears to occur not through the traditional ligand-metal binding but rather ligand-anion interaction. This illustrates how important ligand selection can be for anion stabilization and anion exchange preferences. Throught the modulation of anion preference application specific design can be possible. In Chapter 4 complex CP arrangements are studied, specifically copper 4,4′-bipyridne amino acid CPs. Compared to simpler CPs, the addition of the amino acid allows for additional modulation control. The use of amino acids binding to the Cu center increases aqueous stability through the decrease in solubility. Specifically, amino acids such as L-threonine and L-nitrotyrosine increase the stability of the CPs by higher levels of Cu coordination. This in turn acts as a cross-linker between the Cu-ligand polymer chains.