外围硒环化石墨烯碗的合成及层间组装

厦门大学谭远植团队报道了外围硒环化石墨烯碗的合成及层间组装。相关研究成果发表在2023年2月6日出版的《美国化学会杂志》。

扶手椅边缘石墨核间隔位置的五方环化可以在不破坏六方晶格的情况下构建分子碗。然而，由于不利的应变和所需的多种反应，这种合成仍然具有挑战性。

该文中，研究表明，通过扶手椅边缘的六-邻六苯并科宁的间隔位置处的六重硒环化，构建了一种深度为1.7、直径为1.2nm的新型石墨分子碗。该石墨碗用苯基硒基官能化，在溶液中堆叠成离散的双层二聚体。这种二聚体表现出高稳定性，并在激光消融后在气相中存活。引人注目的是，在固态下观察到具有相干堆叠构型的石墨烯碗的不对称一维超分子柱，这导致了具有显著偏振依赖性的强二次谐波产生。该发现简要地合成了一个具有石墨烯核的巨型分子碗，并证明了扩展石墨烯碗的独特超分子组装。

附：英文原文

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

Author: Zhen-Lin Qiu, Yang Cheng, Qi Zeng, Qiong Wu, Xin-Jing Zhao, Rong-Jie Xie, LiuBin Feng, Kaihui Liu, Yuan-Zhi Tan

Issue&Volume: February 6, 2023

Abstract: 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 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.

DOI: 10.1021/jacs.2c12401

Source: https://pubs.acs.org/doi/10.1021/jacs.2c12401