Degree

Doctor of Philosophy (PhD)

Department

Chemistry

Document Type

Dissertation

Abstract

Metal-organic cages (MOCs) are molecules that consist of metal centers and organic linkers coordinating to build 3D architectures. These MOCs typically have discrete structures and include an accessible inner cavity. The hollow cavities in these molecular cages can host various molecules through encapsulation. Applications of MOCs include sensing, sequestration, detection, separation, drug delivery, and more. The encapsulation process of guest molecules can be driven by various factors such as electrostatic interactions, hydrophobic interactions, or hydrogen bonding. The molecules that can act as guests in MOCs have a wide range of applications. This dissertation work describes two projects based on the properties of cationic MOCs. One project aims to set the stage for encapsulating electrocatalysts, as cages can protect electrocatalysts by minimizing bimolecular deactivation, a common pathway for catalysts to become inactive. At the same time, the other project focuses on sequestering environmental pollutants from the aqueous system with the help of a MOC. In the first project, a pair of Zr-based cationic cages/capsules are used as hosts for the encapsulation of redox-active guests to study the impact of encapsulation on electron transfer in nonaqueous solvents. Anionic transition metal-EDTA complexes are used as probes to monitor the changes in electron transfer properties of the guests in the presence of the MOCs. This work will provide a perspective for future catalyst stabilization. In the second project, a Pd-based MOC is probed to sequestrate four different per- and poly-fluoroalkyl substances (PFAS), a family of emerging pollutants. This work involves monitoring the interaction between the host MOC and guest PFAS in techniques viii such as NMR spectroscopy and ion chromatography and, later, addressing a method of separating PFAS from the aqueous system followed by recycling the host Pd-based MOC.

Date

4-23-2024

Committee Chair

Noemie Elgrishi

Available for download on Tuesday, April 22, 2031

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