Molecular Synthetic Techniques for the Study of Nanoporous Materials
This dissertation documents the development of molecular synthetic techniques for the study of nanoporous materials. Chapter 1 is an introduction to nanoporous materials and reticular chemistry. The concepts to design and synthesize a wide variety of increasingly complex microporous materials for a range of potential applications are discussed. Chapter 2 introduces dehydrobenzannulene (DBA) as a trigonal planar molecule that is useful in approach the synthesis of graphyne materials. A new, efficient synthesis of this building block is presented. Chapter 3 presents the first synthesis of a metal-organic framework (MOF) constructed with a DBA building blocks. The srs topology demonstrates how chiral frameworks can be constructed from achiral organic linkers. The double-walled framework demonstrates the ability to control the orientation of two face-to-face -stacked macrocycles using the microporous framework as a scaffold in crystal engineering. Chapter 4 further investigates the ability to modify the DBA building block in order to control the orientation of two eclipsed -stacked macrocycles in a top-to-bottom fashion resulting in a novel double-walled framework with apo topology. Chapter 5 conclusively demonstrates the robustness of framework design using principles of reticular chemistry to produce a single-walled MOF by modifying the DBA starting material to produce a paddlewheel secondary building unit (SBU) to yield the predicted rht topology. Chapter 6 moves into an organic class of nanoporous materials, covalent organic frameworks (COFs) to extended to other classes of nanoporous materials an alternative form of synthesis, mechanochemical synthesis, to produce the materials predicted by reticular chemisty.