Synthesis and Interlayer Assembly of a Graphenic Bowl with Peripheral Selenium Annulation

作者：Zhen‐Lin Qiu, Yang Cheng, Qi Zeng, Qiong Wu, Xin‐Jing Zhao, Rong-Jie Xie, Liubin Feng, Kaihui Liu, Yuan‐Zhi Tan · 发表于：Journal of the American Chemical Society · 年份：2023 · DOI：10.1021/jacs.2c12401 · 被引用次数：34 · 研究领域：Fullerene Chemistry and Applications、Graphene research and applications、Carbon Nanotubes in Composites

Pentagonal cyclization at the bay positions of armchair-edged graphenic cores can build molecular bowls without the destruction of hexagonal lattices. However, this synthesis remains challenging due to unfavorable strain and the multiple reactions required. Here, we show that a new type of graphenic molecular bowl with a depth of 1.7 Å and a diameter of 1.2 nm is constructed by sextuple Se annulation at the bay positions of armchair-edged hexa-peri-hexabenzocoronene. This graphenic bowl is functionalized with phenylseleno groups that stack into a discrete bilayer dimer in solution. Such a dimer exhibits high stability and survives in the gas phase after laser ablation. Strikingly, the asymmetric one-dimensional supramolecular columns of graphenic bowl with coherent stacking configuration are observed in the solid state, which results in a strong second harmonic generation with prominent polarization dependence. Our findings present a concise synthesis of a giant molecular bowl with a graphenic core and demonstrate the unique supramolecular assembly of extended graphenic bowls.