Title: Organic Electronics Enhanced via Molecular Contortion
Description: Sustainable energy has taken center stage in materials research and global markets, which has encouraged an explosion in related materials development. Practical implementations of sustainable energy solutions rely upon high-performance and cost-effective materials for energy harvesting and storage. Organic electronics, a class of materials composed principally of carbon, are regarded as promising candidates in this respect. Carbon, when arranged with atomic precision and warped carefully into desirable conformations, can generate exceptionally inexpensive and high-performance materials. These materials can then be readily integrated into solar cells, capacitors, and transistors. This dissertation explores our progress in the field of high-performance organic electronics in the context of these practical devices, and aims to establish simple design principles for the future development of contorted organic electronics. Of principal importance to this thesis is the conclusion that localized molecular contortion seems to bestow unique and somewhat unexpected properties upon extended systems.

Therefore, a key theme underlying our work herein is the idea that for specific applications, contorted or extended graphene nanoribbons can be shown to be superior to planar organics. This advantage has allowed us to report exceptionally high performance metrics in the fields of energy harvesting and storage. Chapter 1 comprises an overview of the entire body of work contained within this dissertation, in a highly condensed format. This includes in-depth specific background on the innovations of prior researchers who have enabled our present work. Chapter 2 details the elongation of the small graphene fragment perylene into long, electronically active, and ambient-stable nanoribbons. This chapter is assembled from three research manuscripts investigating the employment of these nanoribbons as electron transporting materials in photovoltaics and one set of preliminary results on their incorporation as potential surface arrays for chip technologies. Chapter 3 examines the expansion of our perylene-based nanoribbons into large single-molecule three-dimensional nanostructures up to 5 nm in wingspan.

These structures, by consequence of their three-dimensional geometry and contorted nature, exhibit curious enhancements over their one-dimensional counterparts. Such enhancements, namely in photovoltaic efficiency and electron transport behavior, are investigated over the course of two research manuscripts. Chapter 4 explores the idea of organic energy storage through the lens of pseudocapacitance, and further expands the perylene toolbox by developing high-capacitance and highly stable polymer structures. These ideas ultimately culminate in the final subchapter, wherein our most recent work on contorted, semi-two-dimensional capacitive polymers is disclosed. The exceptionally strong and potentially economically viable results of our most recent energy storage architecture are enabled entirely by our understanding of molecular contortion. Namely, contortion’s unique ability to manifest long-range electronic conjugation concomitant with the prevention of aggregation, thus improving surface area for ion diffusion and bulk processability.

In consideration of the impact these nanoscale ideas could have on the global scale, it is our belief that ideas concerning contortion within the context of organic electronics will continue to generate high-performance energy storing and harvesting materials. Our explorations towards such solutions have garnered substantial interest in the materials community thus far, and this dissertation seeks to add to that growing body of literature by inspiring numerous new twisted architectures.