Organic semiconductors (OSCs) are low-cost, environmentally friendly alternatives to inorganic semiconductors. With their potential to usher in a new era of sustainable technologies, they are being explored extensively in a diverse variety of applications. Moreover, due to their flexibility and biodegradablity, they provide new functionalities to semiconducting materials such as flexible computer screens, biodegradable electronics (e.g., disposable phones), and energy-harvesting smart materials. Device performance strongly depends on the ease with which charge-carriers move from one molecule to another, which is determined by the solid-state arrangement of the molecules. OSCs tend to be polymorphic, existing in mutiple crystalline packings under ambient conditions. Different crystalline structures, sometimes only with marginal changes to the crystal packing, can have considerably different properties, and consequently polymorphism can be used as a design strategy for high-performance organic electronics. Introducing chirality into organic semiconductors adds another level of functionality as it enables the production of polarization-selective photodetectors, chiroptical switches, and room-temperature spintronic devices. [n]helicenes form a family of archetypal chiral π-conjugated organic molecules that are formed from ortho-fused, angularly arranged benzene rings, where n is the number of aromatic rings in the molecule. Helicenes are promising compounds for designing new organic electronic technologies due to their large chiroptical response, charge-transport properties, and their ability to filter electron spin at room temperature. Chirality adds another level of complexity to the solid-state formation, as chiral compounds can form both enantiopure and racemic crystals with very different electron transport properties. For example, aza [6]helicene has an 80-fold increase in hole mobility in the racemate structure compared to the enantiopure structure. Despite the interest in helicenes, their application in electronic devices remains in its infancy, partly due to a poor understanding of the molecular packing and how it impacts performance. Much of our own work has looked to bridge this gap by using crystal structure prediction (CSP) as a means to develop our understanding of structural motifs that enhance optoelectronic properties. CSP is particularly useful for these molecules due to the inherent rigidity of the structures. In fact, both naphthalene and benzene are used for testing and benchmarking CSP protocols. CSP of helicenes in our own work has helped predict the thin film packings of enantiopure and racemic aza [6]helicene, explaining 80-fold differences in charge mobility. Combining CSP with the prediction of optoelectronic properties can be used to develop energy-structure-function (ESF) maps. We have used this framework to explore the ESF of [6]helicene using CSP. This work highlighted specific structural motifs that were particularly beneficial for either high electron or hole mobility. In an effort to enhance our understanding of the interplay between molecular structure and optoelectronic properties, we have investigated the impact of altering the nitrogen atom's position within aza [6]helicene, while maintaining identical crystal packing. Our findings show that the position of the nitrogen can be crucial in determining the semiconducting properties of the material. Using this prior knowledge of how changes in functional group position and molecular assembly separately affect the charge-carrier mobilities, we screened over 1300 substituted [6]helicenes for high charge mobility. This approach shows promise in guiding the design of new OSC molecular materials and identified fluorinated [6]helicenes as being the most promising to maximize OSC performance metrics. However, it is difficult to outperform unsubstituted helicenes in terms of high charge mobility.