Synthesis, Properties and Noncovalent Control of Bullvalenes

Bullvalene is a fluxional molecule which may undergo Cope rearrangements to interconvert between up to 1,209,600 isomers. This occurs via rapid Cope rearrangements at room temperature due to internal molecular strain. This ability grants access to a dynamic library of structures, from just one isolatable structure. These unique properties have thus far resulted in bullvalene being used in a variety of applications, as the molecule possesses the ability to adapts its isomer distribution to its environment through noncovalent interactions. Due to historic difficulties in its synthesis, collective understanding of bullvalene is limited, however, recent advances in synthesis has made the compound much more accessible. This Thesis discusses bullvalene, as it has been understood since its conception, and explores fundamental details of its rearrangements and shape in 3-D space. Exploration into bullvalene synthesis introduces the challenge of making tetrasubstituted bullvalenes through previously reported methods and altogether novel syntheses. Also, bullvalene is investigated further in a supramolecular context. Alterations of bullvalene’s behaviour due to imposed steric constrains, both intra- and intermolecular, are investigated in an attempt to further explore its unique shapeshifting properties.