The work in this thesis was undertaken to explore both the effect of heteroatoms on the semiconducting properties of star-shaped thienoacenes, and to expand the scope of these materials to fields outside of organic semiconductors. Overall, new star-shaped molecules were prepared with a view towards applications such as thin film transistors, as the organic linker component in metal-organic frameworks, and as ligands that could coordinate to transition metals through the sulfur atom. The first chapter describes the properties of star-shaped molecules, the theory underlying their semiconducting behaviour, and the previous work that motivated the research contained herein. The second chapter of this thesis outlines the synthetic methodology that was utilized to achieve the molecular targets, as well as the characterization techniques that are used to reveal the properties of organic semiconductors. The third chapter of this thesis describes the synthesis and optoelectronic properties of novel nitrogen-containing semiconductor molecules called thienoacridines, and their comparison to carbon-and-sulfur based analogues, thienoanthracenes. The fourth and fifth chapters concern the synthesis of functionalized star shaped thienylbenzene molecules. In Chapter 4, these molecules are decorated with carboxylic acid groups so that they may act as tetrapodal MOF linkers. In Chapter 5, they are equipped with N-aryl(azomethine)thiophene moieties to explore sulfur coordination and act as ligands. The sixth chapter provides conclusion to this work, and possible future directions of the research conducted herein.