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

Allison M Rice; Ekaterina A Dolgopolova; Brandon J Yarbrough; Gabrielle A Leith; Corey R Martin; Kenneth S Stephenson; Rebecca A Heugh; Amy J Brandt; Donna A Chen; Stavros G Karakalos; Mark D Smith; Kelsey B Hatzell; Perry J Pellechia; Sophya Garashchuk; Natalia B Shustova

doi:10.1002/anie.201806202

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

Angew Chem Int Ed Engl. 2018 Aug 27;57(35):11310-11315. doi: 10.1002/anie.201806202. Epub 2018 Jul 30.

Authors

Affiliations

¹ Department of Chemistry and Biochemistry, University of South Carolina (USC), 631 Sumter Street, Columbia, SC, 29208, USA.
² Department of Physics and Astronomy, USC, 712 Main Street, Columbia, SC, 29208, USA.
³ College of Engineering and Computing, USC, 301 Main Street, Columbia, SC, 29208, USA.
⁴ Department of Mechanical Engineering, Vanderbilt University, 2400 Highland Avenue, Nashville, TN, 37212, USA.

PMID: 29974583
DOI: 10.1002/anie.201806202

Abstract

We report the first examples of purely organic donor-acceptor materials with integrated π-bowls (πBs) 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 πB 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 πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.

Keywords: conductivity; corannulene; covalent organic frameworks; photophysics; theoretical calculations.