Doctor of Philosophy (PhD)
The synthesis of conjugated polymers and design of complex materials based on them have become increasingly popular as the demand for low-cost efficient and processible optoelectronic and semiconducting devices escalates. While advanced applications of polymeric materials require some degree of sophistication, success can be achieved through careful consideration of polymerization techniques and methodologies. Controlling critical aspects of the polymerization process allows for synthesis of complex macromolecular architectures possessing unique and novel properties that may be worth of further comprehensive investigation. This dissertation primarily focuses on the development and preparation of well-defined hierarchical macromolecular architectures. The foundation of this work encompasses the transition metal catalytic synthetic methods used to maintain a controlled chain-growth polymerization to yield conjugated polymers. These methods enabled design of a series of novel complex conjugated polymeric materials. A number of intriguing characteristics of these higher ordered polymeric systems are described, in addition to studies on how these characteristics, such as the control of exciton migration enabling modulation of energy transfer, lead to a greater understanding of the fundamental properties inherent of conjugated polymers. While the preparation and synthesis determine the properties of conjugated polymers at the molecular level, supramolecular organization can have even bigger impact on the properties of materials. Investigations into supramolecular organization and structural studies of these organized architectures, while a difficult challenge, were carried out using small-angle neutron scattering and electron microscopy. A last part of this dissertation explores the stereoselective preparation and properties of a novel class of conjugated polymers poly(p-phenylene ethynylene vinylene)s (PPEVs). These materials possess unique spectroscopic and physical properties, such as pronounced mechano-fluorescent behavior, which can be utilized in future optical and sensing devices.
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Chavez, Carlos Anthony, "Development of Transition Metal-Catalyzed Polymerization Reactions and their Applications for the Preparation of Well-Defined Conjugated Polymer Architectures" (2015). LSU Doctoral Dissertations. 2754.
Nesterov, Evgueni E.