The research detailed herein focuses on pore engineering within metal-organic frameworks. Pore size, shape, and chemical properties are key determinants to potential applicability and as such, methods that enable targeted acquisition of these properties warrant thorough exploration. The selection of tetratopic ligands in these studies serve to provide an extra modicum of stability that serves to minimize any structural integrity concerns when evaluating results. Additionally, the efforts in each project rely on the utilization of the post-synthetic modification toolbox. Post-synthetic modifications are valuable methods for tuning pre-existing metal-organic framework structures under milder conditions than those required by solvothermal synthesis - the most common technique for synthesizing these materials. Initially, a foundation is established in which metal-organic frameworks are defined, and their properties discussed. A brief overview of the most common characterization techniques for MOFs is presented to allow for a more critical discussion of the subsequent findings. This is then concluded with a concise summary of current and proposed applications for metal-organic frameworks. Conditions for post-synthetic linker insertions are explored through the installation of secondary linkers into the open sites of a Zr-based metal-organic framework's pores. It is discovered that seemingly trivial differences in linker size and shape may result in noteworthy thermodynamic barriers to insertion and that the success or failure of linker insertion into flexible metal-organic frameworks is indeed controllable through reasonable adjustments to temperatures of insertion. Next, iron-based metal-organic frameworks with minor differences in linker symmetry are constructed, resulting in intriguing differences in pore size and ligand conformation. In order to make these unique structures more practical, post synthetic metal exchange from iron to chromium was utilized in order to strengthen the structure. Following this, the pores of an iron-based metal-organic framework are loaded with urea, thiourea, and commercial fertilizers in order to interrogate their utility as slow-release fertilizers. Successful internalization is verified via powder xray diffraction and thermogravimetric analysis. Finally, a synopsis of the discussed research on pore engineering in metal-organic frameworks well as an opinion on the future directions and outlook of these and related materials is provided.
