Edge Functionalization of Bulk γ-Graphyne Facilitates Mechanical Exfoliation and Modulates the Mode of Sheet Stacking.

We have successfully achieved selective and efficient functionalization of sheet edges in microcrystalline multilayer γ-graphyne through two methods: cross-coupling with residual bromide edge groups and copper-catalyzed azide-alkyne cycloaddition (CuAAC) with edge terminal alkyne groups. This modification significantly enhances the ease of mechanical exfoliation and dispersibility of the sheets of γ-graphyne. Specifically, C-grafted γ-graphyne forms stable dispersions in compatible organic solvents, allowing for the imaging of atomically thin layers of γ-graphyne for the first time.