Synthesis of expanded graphdiyne substructures

Graphdiyne (1) is a member of a novel family of interesting and potentially important allotropes of carbon. Reported herein are the synthesis and spec troscopic characterization of model substructures 2-6. The macrocycles were prepared by the intramolecular cyclization of suitable alpha,omega-polyyne s. Key to the success of this approach was the development of an in situ pr otiodesilylation/alkynylation reaction utilizing reactive phenylbutadiyne s ynthons. This new method has allowed for the preparation of the largest, mo st complete substructures of the graphdiyne network to date (3-6).