Examining the boundaries of strained aryl -aryl coupling reactions in polycyclic aromatic hydrocarbons

Chapter 1. The impact and growth of carbon nanotubes within the framework of nanotechnology is presented. Methods to produce single chirality nanotubes from template-mediated sources are evaluated. The concept of a nanotube endcap is introduced as a potential synthetic target toward the selective synthesis and growth of a single chirality carbon nanotube.;Chapter 2. A modified synthesis of corannulene is presented, highlighting a selective imine based reaction protocol for the fuctionalization 4,7-dimethylacenaphthenequinone. Also reviewed is a cascade coupling approach toward the synthesis of corannulene, followed by an analysis of the thermochemistry of the two-component disconnection.;Chapter 3. The synthesis of 6 different indenoannulated corannulene congeners derived from a single flash vacuum pyrolysis (FVP) is described. X-ray crystal structures for each indenoannulated corannulene are presented along with computational modeling. Spectroscopic comparison between observed and theoretical 1H NMR provides one of the largest complete and comparative data sets for a collection of PAHs.;Chapter 4. The application of a palladium based indenoannulation reaction is presented as an alternative synthetic method to FVP. Heteroatom based derivatives of both tetraindenocorannulene and pentaindenocorannulene were both developed as potential solubilizing factors. The thermochemistry for each successive indenoannulation of 1,3,5,7,9-pentaphenylcorannulene leading to pentaindenocorannulene has been calculated, providing an approximated energy landscape for the total transformation.;Chapter 5. Several routes for the synthesis of 1,3,5,7,9- pentakis(2,6-dichlorophenyl)-corannulene are presented. The yield for this reaction has been improved through the use of a palladium based precatalyst. During this time we studied a five-fold palladium catalyzed borylation of corannulene using B2pin2. Finally development of a cascade coupling reaction towards a [5,5] SWNT endcap is highlighted by a 12 bond coupling reaction.;Chapter 6. A nickel-promoted homo-coupling between the proximally situated aryl halides of 1,2,5,6-tetrakis(2-chlorophenyl)corannulene is used to complete the synthesis of diphenanthro[9,10-a:9',10'- g]corannulene. X-ray quality crystal were grown of diphenanthro[9,10- a:9',10'-g]corannulene, and the structure was solved. The crystals forms highly ordered arrays in a columnar fashion with each phenanthro segment aligned through a series of pi - pi stacking interactions.