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

• DOI: 10.1021/jacs.4c02064
• Publication Date: 2024-05-01T12:39:52Z
• Authors: Claire M. B. Bolding; Tejaswini K. Hara...; Grace L. Parker; William B. Martin; Victor G. Desyatkin; Logan Heck; Konstantin Bukhry...; Valentin O. Rodionov
• Keywords: 01 natural sciences; 0104 chemical sciences

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, C18-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. Additionally, we have discovered that phenylacetylide edge groups alter the preferred stacking mode of γ-graphyne sheets. Few-layer flakes of Ph-edge γ-graphyne exhibit a preference for the symmetric R3m space group, contrasting with the aperiodic stacking of as-synthesized Br-edge γ-graphyne. These results open the door for an easy and scalable exfoliation of few-layer flakes of γ-graphyne with a high aspect ratio, enabling potential applications in carbon electronics.