This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professors Steven H Strauss and Olga V. Boltalina that focuses on the synthesis, isolation, and characterization of a new class of fluorochemical compounds based on fullerenes. Poly(perfluoroalkyl)fullerenes (PFAFs), are thermally (up to 600 C) and chemically stable and yield relatively stable radical anions, which may be isolated and studied as crystalline solids. Series of PFAFs, with varying chain lengths, compositions and structures will be prepared for the in 50-100+ mg quantities using the PIs' high-yield, high-temperature reactions of C60, C70, and other fullerenes with RfI reagents. Other synthetic methodologies will be explored, including substitution of halogen atoms in C60Xn and C70Xn derivatives. These latter reactions may produce kinetic isomers, which will allow the rates and mechanisms of intramolecular isomerization of a series of closely-related fullerene(X)n compounds to be studied in detail for the first time. Reaction conditions will be optimized for compositional and isomeric purity using a dynamic HPLC monitoring technique. The rigid cage structure of PFAFs, in which the Rf groups are attached to sp3 C atoms, will provide a unique opportunity to advance the understanding of through-space Fermi contact coupling between proximate F atoms in rigid sigma-bonded systems.
The stability properties of PFAFs may allow them to be used for optoelectronic and nanoscale electronic devices, which would be explored in a separate collaborative project with NREL. The project involves collaborators in the US and abroad, with whom students will interact, which will broaden student education and help them build networks of professional colleagues.
