Synthesis of a Porous [14]Annulene Graphene Nanoribbon and a Porous [30]Annulene Graphene Nanosheet on Metal Surfaces

作者：Tianchen Qin, Dezhou Guo, Juanjuan Xiong, Xingyu Li, Lei Hu, Weishan Yang, Zijie Chen, Yulun Wu, Honghe Ding, Jun Hu, Qian Xu, Tao Wang, Junfa Zhu · 发表于：Angewandte Chemie International Edition · 年份：2023 · DOI：10.1002/anie.202306368 · 被引用次数：35 · 研究领域：Surface Chemistry and Catalysis、Graphene research and applications、Covalent Organic Framework Applications

The electrical and mechanical properties of graphene-based materials can be tuned by the introduction of nanopores, which are sensitively related to the size, morphology, density, and location of nanopores. The synthesis of low-dimensional graphene nanostructures containing well-defined nonplanar nanopores has been challenging due to the intrinsic steric hindrance. Herein, we report the selective synthesis of one-dimensional (1D) graphene nanoribbons (GNRs) containing periodic nonplanar [14]annulene pores on Ag(111) and two-dimensional (2D) porous graphene nanosheet containing periodic nonplanar [30]annulene pores on Au(111), starting from a same precursor. The formation of distinct products on the two substrates originates from the different thermodynamics and kinetics of coupling reactions. The reaction mechanisms were confirmed by a series of control experiments, and the appropriate thermodynamic and kinetic parameters for optimizing the reaction pathways were proposed. In addition, the combined scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations revealed the electronic structures of porous graphene structures, demonstrating the impact of nonplanar pores on the π-conjugation of molecules.