The impact and role of synthetic chemistry in organic conjugated materials science

Abstract

This dissertation covers broad aspects of synthetic chemistry in organic electronics, from novel molecules to known polymers, from photovoltaics to thermoelectrics, from doped “3D” molecules to doping in nickel coordination polymers. It begins with an introduction to the fundamental aspects of thermoelectrics, with a focus on the role synthetic chemistry plays in developing materials and improving the desired properties. Chapter 2 begins with the importance of performing rigorous syntheses and purifications with a highlight on conjugated polymers by Stille cross-coupling. A detailed explanation of the nontraditional experimental methods and characterization techniques in this dissertation follows. Chapter 3 will describe a new synthetic pathway to thienopyrroledione monomers, a common component in donor-acceptor photovoltaic polymers. Principles of green chemistry and waste reduction highlight the need to optimize reactions conditions while increasing the scope of the available materials. Chapter 4 will present a new class of materials, dithienospirogermoles, and their optoelectronic properties with a focus on electronic behavior of the first and second oxidations. Chapter 5 begins with an overview of nickel-sulfur square-planar complexes and the development of oligomeric coordination compounds of nickel for use as stable n-type organic thermoelectrics. The synthesis of poly(nickel ethenetetrathiolate) (NiETT) through careful selection of reaction conditions that leads to reproducible properties in insoluble oligomers is thoroughly reported. Chapter 6 focuses on the chemical changes happening during NiETT/PVDF composite film annealing through tandem mass spectroscopy-thermogravimetric analysis. The thesis concludes with Chapter 7 which details the synthesis and brief optimization of a structural analog of NiETT, poly(nickel tetrathiooxalate) (NiTTO).