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 spectroscopic characterization of model substructures 2-6. The macrocycles were prepared by the intramolecular cyclization of suitable alpha,omega-polyynes. Key to the success of this approach was the development of an in situ protiodesilylation/alkynylation reaction utilizing reactive phenylbutadiyne synthons. This new method has allowed for the preparation of the largest, most complete substructures of the graphdiyne network to date (3-6).