New methods towards the synthesis of graphene nanoribbons and study of the polymerization of acetylnaphthalene

Chapter 1 describes work towards the synthesis of graphene nanoribbons with varying widths and edge structures. Interest in graphene comes from the high electron mobility at room temperature, exceptional thermal conductivity, and superior mechanical properties.¹ These properties enable graphene’s use in numerous applications such as transparent conducting electrodes, gas detection, transistors, energy storage devices, and polymer composites.¹ Density functional theory has predicted that the electronic properties of GNRs differ with changes in length, width, and differences in edge structure.⁵ First polyacetylene ladder polymers were developed as intermediates for nanoribbons with zig-zag edge structures. Experiments have shown evidence for polyacetylene structures within the material although conversion is too low to be used as a precursor for graphene nanoribbons. Next tetraethynylethene monomers were synthesized to study their use as monomers for Bergman polymerization in hopes of producing armchair edged nanoribbons. Polymers were made with both alkyl and carboxylic acid functionality. ortho-Acylphenols are useful reagents in the synthesis of many natural products, pharmaceuticals, agrichemicals, flavors, and fragrances²⁷,²⁸. For this reason, ketone directed hydroxylation of arenes catalyzed by Pd was developed by Dong and coworkers. During this work it was discovered that 1-acetylnaphthalene would polymerize under the reaction conditions. Chapter 2 describes the author’s efforts to understand the polymerization mechanism through the synthesis of a variety of substituted acetylnaphthalene derivatives and their polymerization.