The synthesis and properties of corannulene and novel corannulene derivatives

The recent synthesis of macroscopic quantities of buckminsterfullerene and higher fullerenes has stimulated a renaissance of interest in polycyclic aromatic hydrocarbon (PAH) chemistry, specifically focused on the class of curved PAHs for which a significant portion of the molecular structure can be “mapped” onto a fullerene skeleton. Corannulene, a C₂₀ H₁₀ fragment of buckminsterfullerene, is the smallest member of this class that retains the curvature of its parent. This dissertation will address four areas of corannulene research: (1) the improved synthesis of the corannulene core, (2) reactions of halocorannulene derivatives, (3) synthesis of novel fluoranthenes for potential conversion to corannulene derivatives, and (4) organometallic η2/η 1 silver (I) complexes of corannulene.*; An improved five-step, solution-phase synthesis of corannulene now allows large-scale production, and slight variations allow the production of new derivatives.*; The five-fold symmetry and novel dynamic properties of corannulene make its sym-pentasubstituted derivatives attractive targets as building blocks for larger molecular architectures. Regiochemical control and functional group generality are two hurdles to overcome in the synthesis of superstructures based on the five-fold symmetry of corannulene. Fortuitously, chlorination of corannulene with iodine monochloride yields sym-pentachlorocorannulene thus providing a starting point for further synthetic transformation. The systematic conversion of pentachlorocorannulene into a variety of sym-pentasubstituted corannulene derivatives and the study of their dynamic properties uncovers a special cooperative interaction of functional groups around the rim of the bowl.*; The synthesis of novel fluoranthenes for potential conversion to corannulene derivatives has been accomplished by several different routes, highlighted by the use of acetylenes as Diels-Alder partners and a novel tetracyano fluoranthene derivative obtained via a Knoevenagel condensation.*; The reactivity of metals with curved PAHs has been the subject of substantial research. Due to its commercial availability, the bulk of this effort has been directed to the study of buckminsterfullerene, but the reactivity of higher order fullerenes and buckybowls has also been studied. The synthesis of four different organometallic η2/η1 silver (I) complexes of corannulene has been accomplished. The use of different counterions results in a drastic variation in the overall three-dimensional connectivity of the crystal framework.; *Please refer to dissertation for diagrams.