Corannulene: A Curved Polyarene Building Block for the Construction of Functional Materials.

Abstract

This Account describes a body of research in the design and synthesis of molecular materials prepared from corannulene. Corannulene (C20H10) is a molecular bowl of carbon that can be visualized as the hydrogen-terminated cap of buckminsterfullerene. Due to this structural resemblance, it is often referred to as a buckybowl. The bowl can invert, accept electrons, and form host-guest complexes. Due to these characteristics, corannulene presents a useful building block in materials chemistry.In macromolecular science, for example, assembly of amphiphilic copolymers carrying a hydrophobic corannulene block enables micelle formation in water. Such micellar nanostructures can host large amounts of fullerenes (C60 and C70) in their corannulene-rich core through complementarity of the curved π-surfaces. Covalent stabilization of the assembled structures then leads to the formation of robust water-soluble fullerene nanoparticles. Alternatively, use of corannulene in a polymer backbone allows for the preparation of electronic and redox-active materials. Finally, a corannulene core enables polymer chains to respond to solution temperature changes and form macroscopic fibrillar structures. In this way, the corannulene motif brings a variety of properties to the polymeric materials.In the design of non-fullerene electron acceptors, corannulene is emerging as a promising aromatic scaffold. In this regard, placement of sulfur atoms along the rim can cause an anodic shift in the molecular reduction potential. Oxidation of the sulfur atoms can further enhance this shift. Thus, a variation in the number, placement, and oxidation state of the sulfur atoms can create electron acceptors of tunable and high strengths. An advantage of this molecular design is that material solubility can also be tuned. For example, water-soluble electron acceptors can be created and are shown to improve the moisture resistance of perovskite solar cells.Host-guest complexation between corannulene and γ-cyclodextrin under flow conditions of a microfluidic chamber allows for the preparation of water-soluble nanoparticles. Due to an oligosaccharide-based sugarcoat, the nanoparticles are biocompatible while the corannulene component renders them active toward nonlinear absorption and emission properties. Together, these attributes allow the nanoparticles to be used as two-photon imaging probes in cancer cells.Finally, aromatic extension of the corannulene nucleus is seen as a potential route to nonplanar nanographenes. Typically, such endeavors rely upon gas-phase synthesis or metal-catalyzed coupling protocols. Recently, two new approaches have been established in this regard. Photochemically induced oxidative cyclization, the Mallory reaction, is shown to be a general method to access corannulenes with an extended π-framework. Alternatively, solid-state ball milling can achieve this goal in a highly efficient manner. These new protocols bring practicality and sustainability to the rapidly growing area of corannulene-based nanographenes.In essence, corannulene presents a unique building block in the construction of functional materials. In this Account, we trace our own efforts in the field and point toward the challenges and future prospects of this area of research.