Synthesis and use of reactive molecular precursors for the preparation of carbon nanomaterials

The use of reactive molecular carbon precursors is required if the preparation of carbon nanostructures and nanomaterials is to be achieved under conditions that are sufficiently benign to control their nanoscopic morphology and tailor their chemical functionalization. Recently, oligoyne precursors have been explored for this purpose, as they are sufficiently stable to be available in tangible quantities but readily rearrange in reactions that yield other forms of carbon. In this chapter, we briefly discuss available synthetic routes toward higher oligoynes that mostly rely on transition metal-mediated coupling reactions. Thereafter, a comprehensive overview of the use of oligoyne derivatives as precursors for carbon nanostructures and nanomaterials is given. While the non-templated conversion of simple oligoynes into carbonaceous matter exemplifies their potential as metastable carbon precursors, the more recent attempts to use functionalized oligoynes in host-guest complexes, self-assembled aggregates, thin films, colloids or other types of supramolecular structures have paved the way toward a new generation of carbon nanomaterials with predictable nanoscopic morphology and chemical functionalization.