Date of Award
Chemistry and Biochemistry
Inorganic, Materials, Metal-Ligand, Organic, Polymer, Semiconducting Material
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This work is licensed under a Creative Commons Attribution 4.0 International License.
Over the years, the development of materials has seen a vast amount of expansion into a variety of disciplines which have demonstrated usefulness in a large span of applications. One of these new and developing themes is the use of metals and ligands which are incorporated into polymers to modify their properties, which can enable different desired properties. Incorporation of metal-ligand complexes in materials chemistry has proven to be an area of rising interest, however, many of these interactions and systems remained completely unexplored. Understanding the key fundamental principles of how these materials can be changed and modified through metal-ligand inclusion can greatly increase the efficiency and output of future implemented technologies. Also, the involvement and incorporation of transition metals can also bring about sought after properties such as autonomous self-healing, which is the ability for a damaged device to repair itself without any external stimuli, which is directly due to the corresponding bond strengths and interactions respectively. These property modifications are brought about by the dynamic interactions between the metal and ligand, changing their electronic properties and bonding strengths, drastically altering a material’s characteristics. Therefore, this dissertation will primarily focus on metal-ligand interactions in semiconducting π-conjugated materials, and will investigate the physical, chemical, optoelectronic, and morphological changes induced by transition metal chemistry and their dynamic interactions. Accordingly, chapter 1 will outline a general overview and introduction to semiconducting polymers, which includes their applications in organic electronics, device fabrication and function, and will comprehensively introduce the metal-ligand chemistry relevant to materials chemistry. Chapter 2 highlights the functionality of metal-ligand complexes incorporated into semiconducting π-conjugated polymers, which demonstrate the ability to enhance charge mobility values when fabricated into an OFET device. The systems properties were thoroughly investigated and revealed many unique observations. Chapter 3 breaks down elementary building blocks of what compromises the polymer presented in the previous chapter, and through slight modifications demonstrates that these primary sub-units can form supramolecular materials through complexation of the metal through pendant sidechains of the π-conjugated building block. Characterization of these supramolecular materials proved challenging, however were confirmed through a multitude of optoelectronic characterization techniques. Chapter 4 and Chapter 5 investigates different avenues of modifying organic dyes or pigments which are commonly utilized in semiconducting polymer chemistry to generate organic-inorganic hybrids which incorporate metal inclusion directly to the organic pigment itself. Through this facile complexation method, it has been demonstrated that the optoelectronic and physical properties of the dyes are significantly modified. For example, solubilities of these organic dyes are rather poor in common organic solvents, however, when complexed with a metal directly, these materials become soluble in a wide array of organic solvents, greatly improving the processability of the organic pigment material. Lastly, chapter 6 will summarize the key findings unveiled along the dissertation and will also highlight the potential future of these new metal-containing materials, as well as their potential in emergent applications in organic electronics.
St Onge, Peter Blake Joseph, "Dynamic Metal-Ligand Interactions in Semiconducting π-Conjugated Materials" (2024). Electronic Theses and Dissertations. 9146.