Synthesis of Porous Carbon‐Based Network Containing Ultra‐Narrow Nonplanar Nanopores on Surfaces

Introduction of twisted structures into low‐dimensional graphene‐based nanostructures has important ramifications on their inherent physical behavior. The fabrication of graphene derivatives with nonplanar characteristics remains challenging, especially for extended two‐dimensional (2D) structures. Herein, we report the synthesis of a novel nonplanar [32]annulene porous carbon‐based network that contains the narrowest periodic nanopores and exhibits the highest negative curvature among 2D nonplanar carbon‐based nanostructures synthesized up to date. The success is driven by the dissymmetrical debromination and regioselective coupling reactions of precursor molecules on a Au(111) surface, as corroborated by scanning tunneling microscopy (STM) and synchrotron radiation photoemission spectroscopy (SRPES). We characterize electronic properties of the [32]annulene porous carbon‐based network with the aid of scanning tunneling spectroscopy (STS), and demonstrate a significant hole doping induced by interfacial charge transfer between the nonplanar nanoarchitecture and the Au(111) substrate.