The research presented in this dissertation describes the design and synthesis of substitutional-solid-solution-based multivariate metal-organic frameworks (SSS-based MTV MOFs) with functionalized organic linkers to study their emergent properties in the crystalline solid state. The synthetic versatility and tunability of organic chemistry coupled with the predictable organization of inorganic structures enables MTV MOF systems to further the fundamental understanding of structure-composition-property relationships for the targeted design of applied materials due to their ability to control the structure, composition, and property independently. To begin, a set of terphenyl linkers with varied steric and electronic properties were crystallized as a family of UiO-type MOFs to assess their effects on the uptake and separation of noble gases. This series was then isoreticularly expanded to PEPEP linkers and combined in a PIZOF-type MTV MOF system to evaluate its capability as a multivariate platform for linkers with different functional groups. Chapters 4, 5, and 6 each focus on a different advantageous aspect of the PIZOF system, first exploring the free volume in the pores where covalently bound redox active mediators demonstrate electron diffusion via charge-hopping mechanics to achieve redox conductivity. The next chapter studies the aggregate-induced emission properties that can arise from link-link interactions due to the interpenetrated structure of PIZOF-type frameworks by incorporating a pentacene-based linker in an MTV MOF series to determine its singlet fission potential. The last chapter utilizes the water stability of the PIZOF framework to investigate how increasing pore hydrophilicity through the inclusion of a rationally designed pentaerythritol-containing linker affects the water adsorption. This dissertation demonstrates the value of the SSS-based MTV MOF approach under the paradigm of reticular chemistry to enable the design of tunable and complex solid-state systems with the ability to deconvolute structure from composition and property, while still allowing for relationships between the structure, composition, and property.
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Uribe Romo, Fernando
Doctor of Philosophy (Ph.D.)
College of Sciences
Length of Campus-only Access
Doctoral Dissertation (Campus-only Access)
Fairchild, David, "Reticular Design and Synthesis of Metal-Organic Frameworks with Targeted Emergent Properties" (2022). Electronic Theses and Dissertations, 2020-. 1558.
Restricted to the UCF community until February 2024; it will then be open access.