Abstract
Metal-organic frameworks (MOFs) that form in nets featuring only one edge position (edge-1-transitive) for linker incorporation are amenable for the homogeneous distribution of multicomponent link mixtures to form multivariates (MTV). From Vegard's law, edge-1-transitive MTV MOFs offer a high degree of predictability and provide a unique avenue to deconvolute structure-property relationships. Using zirconia MOFs that form in predictable topologies, we can reliably access targeted crystallographic parameters by mixing homeomorphic links with varying metrics. This strategy allows for precise control over both functionality and metrics independently. We can use similar strategies toward the design of MOFs with targeted properties like photocatalysis. Since MOFs based on titania secondary building units exhibit exceptional photoredox activity, we use this MTV approach to prepare a new library of photoredox active titania MOFs (UCFMOF-n, where n = # of phenyl rings in the link). UCFMOFs feature high substrate uptake which, in combination with light harvesting functionalization, results in superior visible light driven oxidation of benzyl alcohol. This work outlines strategies for combining continuous isoreticular expansions with link functionality to systematically study MOFs as complex materials. We show that by utilizing reticular chemistry strategies to synthesize MOFs we can predict both structure and properties based solely on the building blocks used and their molar ratios. These strategies allow us to design new crystalline materials with targeted function, and deconvolute structure-property relationships that typically govern solid state material properties.
Notes
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Graduation Date
2023
Semester
Summer
Advisor
Uribe Romo, Fernando
Degree
Doctor of Philosophy (Ph.D.)
College
College of Sciences
Department
Chemistry
Degree Program
Chemistry
Identifier
CFE0009700; DP0027807
URL
https://purls.library.ucf.edu/go/DP0027807
Language
English
Release Date
August 2024
Length of Campus-only Access
1 year
Access Status
Doctoral Dissertation (Campus-only Access)
STARS Citation
Bryant, Jacob, "Leveraging the Principles of Reticular Chemistry for the Design of Crystallographically and Chemically Complex Multivariate Frameworks" (2023). Electronic Theses and Dissertations, 2020-2023. 1854.
https://stars.library.ucf.edu/etd2020/1854
Restricted to the UCF community until August 2024; it will then be open access.