Indenocorannulene-Based Materials: Effect of Solid-State Packing and Intermolecular Interactions on Optoelectronic Properties

Curved carbon a-systems, such as indenoorannulenes (2-5) with tunable structural and electronic properties are attractive targets for a new class of active components, in molecular devices. The significant curvature of these components favors the formation of columnar stacking in the crystal and confines the electronic states anisotropically on the nanoscale, thus imparting important physical characteristics. Pentaindenocorannulene (C50H20), 5, a deep bowl polynuclear aromatic hydrocarbon, has recently been found to form two polymorphic "solvate" structures, which pack quite differently in the crystalline material and therefore manifest significantly different materials properties. Formation of electronic excitations via excitons is sensitive to the specifics of the packing geometry, such as the degree of a-system overlap, and plays a role in determining the associated optical and transport properties. The present investigation addresses details of the structure and packing of these bowl structures as well as aggregate forms using high-level dispersion-enabled density functional theory. Additionally, use of state-of-the-art first-principles many-body GW-BSE theory provides detailed analysis of their optoelectronic properties in the solid.