Carbon networks based on dehydrobenzoannulenes. 5. Extension of two-dimensional conjugation in graphdiyne nanoarchitectures.
[structures: see text] The synthesis and optical properties of a series of multinanometer-sized substructures of the phenyl-diacetylene carbon allotrope, graphdiyne, are described. These molecules are among the largest and most complex annulenic systems yet prepared, with extension of linear conjugation in two-dimensions to over twice that of any previously reported planar macrocycle. The graphdiyne substructures are constructed through convergent syntheses, taking advantage of three key intermediates and silane-protected phenylacetylenes. Intramolecular macrocyclization of alpha,omega-polyyne precursors via Cu-mediated or Pd-catalyzed oxidative homocoupling affords five new graphdiyne "oligomers" possessing two to four fused 18-membered rings. The attempted synthesis of a six-ring analogue is also reported.
Marsden
Jeremiah A
JA
Department of Chemistry, Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA.
Haley
Michael M
MM
D000114:Acetylene / Q000031:analogs & derivatives* / Q000737:chemistry; D001555:Benzene Derivatives / Q000138:chemical synthesis / Q000737:chemistry; D006841:Hydrocarbons, Aromatic / Q000138:chemical synthesis* / Q000737:chemistry; D006844:Hydrocarbons, Cyclic / Q000737:chemistry; D049329:Nanostructures / Q000737:chemistry*
D001555:Benzene Derivatives; D006841:Hydrocarbons, Aromatic; D006844:Hydrocarbons, Cyclic; C044736:phenylacetylene; D000114:Acetylene