Stack the Bowls: Tailoring the Electronic Structure of Corannulene-Integrated Crystalline Materials

We report the first examples of purely organic donor-acceptor materials with integrated pi-bowls (pi Bs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four-orders-of-magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne-azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual pi B orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for pi B utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.