dc.contributor.advisor | Powers, David | |
dc.creator | Ezazi, Andrew A. | |
dc.date.accessioned | 2023-10-12T13:56:33Z | |
dc.date.available | 2023-10-12T13:56:33Z | |
dc.date.created | 2023-08 | |
dc.date.issued | 2023-07-10 | |
dc.date.submitted | August 2023 | |
dc.identifier.uri | https://hdl.handle.net/1969.1/199863 | |
dc.description.abstract | Reactive intermediates invoked in the functionalization of strong C-H bonds are difficult to characterize. The high energy required to break C-H bonds often means the lifetime of the intermediates is fleeting due to opportunities to engage in undesired reactivity. One method of suppressing undesired reactivity pathways is to immobilize the reactive intermediate in a solid. While doing so may result in longer-lived intermediates, ensconcing a molecule in a material introduces other issues, namely several homogeneous characterization methods are unavailable in the context of heterogeneous materials.
This dissertation will present efforts to develop new materials to immobilize and characterize reactive nitride intermediates. The first chapter discusses strategies to synthesize Metal-Organic Frameworks (MOFs) based on kinetically inert ions. In the second chapter, we leverage the metalloligand strategy advanced in the first chapter to synthesize new MOFs based on Ru2 paddlewheel molecules, which we hope will serve as platforms to interrogate nitrogen atom transfer in confined environments. The third chapter discusses the synthesis of optically transparent thin films of Ru2 paddlewheel molecules, their photochemistry, and attempts at apical ligand metathesis to introduce photoprecursor groups. The fourth chapter builds upon the synthesis of porous, optically transparent thin films demonstrated in the third chapter, but instead with porphyrin molecules. We explored the growth mechanism of our polyelectrolyte films and explore solid-state photochemistry of our films. The final chapter presents a prospectus of future film targets for solid-state photochemistry. | |
dc.format.mimetype | application/pdf | |
dc.language.iso | en | |
dc.subject | Photochemistry | |
dc.subject | thin films | |
dc.subject | layer-by-layer | |
dc.subject | Metal-organic Frameworks | |
dc.subject | reactive intermediates | |
dc.subject | photochemistry | |
dc.title | New Materials for the Immobilization, Generation, and Characterization of Reactive Intermediates | |
dc.type | Thesis | |
thesis.degree.department | Chemistry | |
thesis.degree.discipline | Chemistry | |
thesis.degree.grantor | Texas A&M University | |
thesis.degree.name | Doctor of Philosophy | |
thesis.degree.level | Doctoral | |
dc.contributor.committeeMember | Banerjee, Sarbajit | |
dc.contributor.committeeMember | Zhou, Hongcai | |
dc.contributor.committeeMember | Shetty, Manish | |
dc.type.material | text | |
dc.date.updated | 2023-10-12T13:56:34Z | |
local.etdauthor.orcid | 0000-0002-3884-3500 | |