Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Organic Solids, Institute of Chemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China.
University of Chinese Academy of Sciences, Beijing 100049, PR China.
J Am Chem Soc. 2023 Mar 8;145(9):5400-5409. doi: 10.1021/jacs.2c13604. Epub 2023 Feb 21.
Graphdiyne, a sp- and sp-hybridized 2D π-conjugated carbon material with well-dispersed pores and unique electronic properties, was well investigated and applied in catalysis, electronics, optics, and energy storage and conversion. Graphdiyne fragments with conjugation in 2D can provide in-depth insights for understanding the intrinsic structure-property relationships of graphdiyne. Herein, an atomic precise wheel-shaped nanographdiyne composed of six dehydrobenzo [18] annulenes ([18]DBAs, the smallest macrocyclic unit of graphdiyne), was realized through the sixfold intramolecular Eglinton coupling in the hexabutadiyne precursors obtained by the sixfold Cadiot-Chodkiewicz cross-coupling of hexaethynylbenzene. Its planar structure was revealed by X-ray crystallographic analysis. The full cross-conjugation of the six 18π electron circuits yields the π-electron conjugation along the giant π core. This work provides a realizable method for the synthesis of future graphdiyne fragments with different functional groups and/or heteroatom doping, as well as the study of the unique electronic/photophysical properties and aggregation behavior of graphdiyne.
二维 sp 和 sp2 杂化的π共轭碳材料石墨炔具有良好的分散性孔隙和独特的电子特性，在催化、电子、光学、储能和转换等领域得到了广泛的研究和应用。二维共轭的石墨炔片段可以为深入了解石墨炔的内在结构-性能关系提供深入的见解。在此，通过六倍分子内 Eglinton 偶联，实现了由六个去氢苯并[18]轮烯([18]DBA，石墨炔的最小大环单元)组成的原子精确轮状纳米石墨炔。通过六倍 Cadiot-Chodkiewicz 交叉偶联六乙炔基苯得到的六丁二炔前体。其平面结构通过 X 射线晶体学分析揭示。六个 18π 电子环的完全交叉共轭产生了沿巨大π核的π电子共轭。这项工作为具有不同官能团和/或杂原子掺杂的未来石墨炔片段的合成以及对石墨炔独特的电子/光物理性质和聚集行为的研究提供了一种可行的方法。
