Guo Shen-Yi, Zhang Zhuo-Ang, Tong Shuo, Guo Qing-Hui, Hua Ruimao, Wang Mei-Xiang
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (MOE), Department of Chemistry, Tsinghua University Beijing 100084 China
Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University Hangzhou 310027 China
Chem Sci. 2023 Jul 11;14(31):8393-8400. doi: 10.1039/d3sc02417b. eCollection 2023 Aug 9.
In contrast to a plethora of macrocyclic and cage compounds, spirophanes have remained largely unexplored. We report herein the construction, structure and properties of unprecedented tetrahomo corona[4]arene-based ditopic and tritopic macrocycles of spiro structures. Synthesis was conveniently achieved by means of an efficient SAr reaction from simple and commercially available starting materials. Racemic samples were resolved into enantiopure chiral tetrahomo -corona[4]arenes, spirophanes and bispirophanes which show interesting chiroptical properties. The acquired electron-deficient macrocyclic compounds were found to adopt unique conformational structures and to form distinct complexes with TTF in the solid state. Our study provides a new opportunity to develop multitopic macrocycles of different topologies which have potential applications in supramolecular chemistry.
与大量的大环化合物和笼状化合物不同，螺环芳烃在很大程度上仍未被探索。我们在此报告了前所未有的基于四同系物冠[4]芳烃的具有螺环结构的双位点和三位点大环化合物的构建、结构和性质。通过从简单且市售的起始原料进行高效的亲核芳香取代反应，方便地实现了合成。外消旋样品被拆分为对映体纯的手性四同系物冠[4]芳烃、螺环芳烃和双螺环芳烃，它们表现出有趣的手性光学性质。发现所获得的缺电子大环化合物具有独特的构象结构，并在固态下与四硫富瓦烯形成独特的配合物。我们的研究为开发具有不同拓扑结构的多位点大环化合物提供了新机会，这些大环化合物在超分子化学中具有潜在应用。
