Contorted and Strained Molecular Nanographenes: Multi-Electron Storage and Reduction-Induced Transformations

With the support of the Macromolecular, Supramolecular and Nanochemistry (MSN) program in the Division of Chemistry, Professor Marina A. Petrukhina of the University at Albany is studying charge-transfer effects in the emerging classes of highly warped and twisted nanographene scaffolds to promote their use as critical components in energy storage, conducting and quantum computing devices. Through systematic studies, the project aims to provide insights into multi-electron storage abilities of topologically different nanocarbon hosts upon stepwise chemical reduction. If successful, the knowledge gained will provide guiding principles for the design of new molecular and supramolecular carbon materials and their respective electronic, magnetic, and intercalation properties for technologically important applications. This project will also provide educational and training opportunities for graduate and undergraduate students at the University at Albany. Students will be exposed to a broad range of science including organic and organometallic synthesis, supramolecular assembly, solution and solvent-free crystal growths, X-ray diffraction and spectroscopic characterization methods. Outreach and community engagement activities will build on the new Emerging Technology and Entrepreneurship Complex facility at the university and the summer research program “Playing with Carbon Balls, Bowls, Hoops and More” designed for undergraduate and high school students. In this project, a variety of structurally well-defined nanographenes with contorted and strained carbon frameworks will be selected for investigation of their multi-electron acquisition and storage abilities. Using controlled chemical reduction methods, the electronic and structural consequences of the stepwise injection of negative charge and spin into pi-conjugated nanographene systems will be systematically evaluated. More specifically, the effects of altering geometry, functionalization, and strain at the molecular level will be analyzed with an eye toward identifying systems with enhanced electron storage abilities. Additionally, structural transformations of nanographenes with embedded odd-membered rings upon multi-electron charging will be examined and the utility of creating localized spin-density and anti-aromatic spots for inducing site-specific reactivity will be tested. The project will also probe if the reduction-mediated annulation approach can be utilized for controlled build-up of pi-extended nanocarbon frameworks. This research seeks to address fundamental chemistry questions of relevance to charge transfer in graphitic materials that are important for the development of the next generation of optoelectronic and energy storage devices. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.