Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084 (China).
Angew Chem Int Ed Engl. 2014 Dec 1;53(49):13548-52. doi: 10.1002/anie.201407670. Epub 2014 Oct 8.
O6 -Corona[3]arene[3]tetraazines, a new class of macrocyclic compounds, were synthesized efficiently in a one-pot reaction from the nucleophilic aromatic substitution reaction between 1,4-dihydroxybenzene derivatives and 3,6-dichlorotetrazine in warm acetonitrile. In the crystalline structure, the resulting macrocycles adopt highly symmetric structures of a regular hexagonal cavity with all bridging oxygen atoms and tetrazine rings located on the same plane with phenylene units orthogonally orientated. The constitutional aromatic rings are able to rotate around the macrocyclic annulus, depending on the steric effect of the substituents and temperature, in solution. The electron-deficient nature revealed by cyclic voltammetry, differential pulse voltammetry, and characteristic absorbances at a visible region show the O6 -corona[3]arene[3]tetrazines to be suitable macrocyclic receptors for electron-rich guests.
O6-冠[3]芳烃[3]四嗪是一类新的大环化合物，可通过 1,4-二羟基苯衍生物与 3,6-二氯四嗪之间的亲核芳香取代反应在温热的乙腈中一锅法高效合成。在晶体结构中，所得大环化合物采用高度对称的规则六边形腔结构，所有桥连氧原子和四嗪环位于同一平面上，与苯环单元正交取向。在溶液中，根据取代基和温度的空间位阻效应，构成的芳香环可以围绕大环环系旋转。循环伏安法、差分脉冲伏安法和可见区域特征吸收所揭示的缺电子性质表明，O6-冠[3]芳烃[3]四嗪适合作为富电子客体的大环受体。
