Tuning the properties of porous coordination cages via ligand design

Abstract

Chapter 2 illustrates the influence of various amide substituents on the physical properties of cuboctahedral cages. The crystallographic packing structure is dependent on what substituents are present, and as such the accessible surface area, solubility, and stability of the final product are affected. An advantage to soluble coordination cages is their ability to crystallize differently depending on what solvent is used, which allows for tunable density. ☐ Chapter 3 investigates the use of mechanochemistry to synthesize porous metal-organic materials in the absence of solvent. There are economic and environmental incentives to reduce the use of coordinating solvents when synthesizing proous materials, but no coordination cage has successfully been fabricated this way until now. ☐ Chapter 4 describes the synthesis and characterization of low nuclearity coordination cages. Here, the smallest possible paddlewheel-based coordination cage was synthesized and discovered to exhibit appreciable porosity to carbon dioxide compared to larger porous coordination cages. ☐ Chapter 5 investigates the use of solution-state characterization strategies as a method of identifying supramolecular structures in solution. Materials that potentially isomerize or decompose in solution are difficult to characterize with traditional methods. This chapter lists a systematic approach to diffusion NMR spectroscopy, transmission electron microscopy, and cryo transmission microscopy as a method of identifying cage structures in solution.