Dissertation/Thesis Abstract

Synthesis and Application of Styryl Phosphonic and Cinnamic Acid Derivatives
by McNichols, Brett William, Ph.D., Colorado School of Mines, 2017, 282; 10624231
Abstract (Summary)

Styryl phosphonic and cinnamic acid derivatives have been gaining attention as key candidates to modulate specific electrode properties in organic electronic devices such as work function, surface energies, wettability, and electron charge transfer kinetics that lead to increased efficiency, operational range, and device lifetimes. Very few of these acids are commercially available. The driving factor behind this research is to explore simple, high yield, and inexpensive synthetic routes towards synthesis of these acids. Herein, the novel synthesis of vinyl phosphonic acids (VPAs) and their subsequent influence on interface properties compared to their phenyl phosphonic acids (PPAs) and benzyl phosphonic acids (BPAs) analogues are explored. This includes an in depth comparison of varying polar VPA, BPA, and PPA “families” attachment on conductive oxides as they allow for careful work function tuning of band edge energy and chemical properties on these surfaces.

By leveraging similar techniques of VPA synthesis we can produce analogous cinnamic acids in which these same surface control concepts are applied on the surface of lead sulfide (PbS) colloidal semiconductor nano-crystals, or quantum dots (QDs). In order to do this, first a development of a simple solution-phase ligand exchange was necessary, from which we selectively replace native solubilizing ligands with these fictionalized cinnamic acids. This application achieved remarkable control allowing the band edge position to be tuned over an unprecedented 2.0 eV.

This cinnamic acid synthetic chemistry can then be extended to functionalize multi acrylate containing molecules creating organic linkers to be integrated into Metal Organic Frameworks (MOFs). MOFs have increasingly gained attention for many high impact applications including but not limited to catalysis, gas storage and release, sensors, energy harvesting, conductivity, and filtration. A great amount of research is presently being conducted in developing new MOFs from the same handful of commercially available linkers. We introduce synthetic techniques for 18 isoreticular series of linkers that can be formulated with similar, if not identical, conditions giving way to the formation of previously unknown frameworks. This technique led us to incorporate a number of these linkers into Ni-MOFs and investigate catalytic activity for conversion of oleic acid to liquid hydrocarbons.

Indexing (document details)
Advisor: Sellinger, Alan
Commitee: Pylypenko, Svitlana, Yang, Yongan, Zimmerman, Jeramy
School: Colorado School of Mines
Department: Chemistry and Geochemistry
School Location: United States -- Colorado
Source: DAI-B 79/02(E), Dissertation Abstracts International
Source Type: DISSERTATION
Subjects: Organic chemistry
Keywords: Cinnamic acid, Metal organic framework, Organic synthesis, Phosphonic acid, Quantum dot, Work function
Publication Number: 10624231
ISBN: 978-0-355-39926-4
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