The goal of this thesis is to synthesize libraries of organic building blocks with systematic functionalizations for tuning dynamics and steric traits in crystalline frameworks. Chapter 1 will introduce the materials being studied, their targeted applications, and a brief outline of each chapter will also be included. Chapters 2 explores the impact of mechanical processing in Covalent Organic Frameworks (COFs) from the point of view of crystallographic effects and pressure induced preferred orientation. This chapter also studies solid-state ionic conduction for Li ions in crystallographically aligned COFs studied by solid-state NMR and Electrochemical Impedance Spectroscopy (EIS), we observed fast ionic conduction. Chapter 3 involves the synthesis of a family of COFs with highly mobile side chains of variable length to understand amphidynamic behavior in these materials. This amphidynamic behavior is studied through ssNMR relaxometry to probe the relationship between the pore dynamics and the framework. Chapter 4 is the synthesis of titania Metal Organic Frameworks (Ti-MOFs) with systematically expanded links for understanding the pore steric effects of small molecule transfomations in photoredox catalysis. This expanded steric effects showed improvements in kinetic conversions from 20 % to 80 %, in the oxidation of benzyl alcohol. Throughout this thesis it is demonstrated how synthetic control of the molecular traits of the organic components of these reticular materials can have not only precise tuning of the structure but also control their properties.
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Uribe Romo, Fernando
Doctor of Philosophy (Ph.D.)
College of Sciences
Length of Campus-only Access
Doctoral Dissertation (Open Access)
Vazquez-Molina, Demetrius, "Tuning Dynamics, Sterics, and Ion Conductivities in Reticular Materials" (2020). Electronic Theses and Dissertations, 2020-. 460.