Sun Shijun, Liu Zhen, Colombo Francesca, Gao Rui, Yu Yuming, Qiu Yi, Su Jie, Gan Liangbing
State Key Laboratory of Chemistry and Utilization of Carbon-Based Energy Resources, College of Chemistry, Xinjiang University, 830017, Urumqi, Xinjiang, P. R. China.
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, 100871, Beijing, China.
Angew Chem Int Ed Engl. 2022 Dec 23;61(52):e202212090. doi: 10.1002/anie.202212090. Epub 2022 Nov 27.
A 19-membered open-cage fullerene derivative was prepared from C in 7 steps and 5.5 % yield through the peroxide-mediate pathway. There are four carbonyl groups, an ether oxygen and a quinoxaline moiety on the rim of the orifice. A chloride anion could be inserted into its cavity by heating with hydrochloric acid at 60 °C for 4 h. Encapsulation of fluoride, bromide and iodide anions was also achieved at slightly more forcing conditions, 90 °C for 14 h. Single crystal X-ray structures of the sodium salt of the chloride and the bromide encapsulated derivatives were obtained, which showed the halide anion in the center of the cavity and two sodium cations connecting two cages through coordination to the oxygen atoms on the rim of the orifices. The halide encapsulation ratio is quantitative in the isolated products.
通过过氧化物介导的途径，以C为原料，经过7步反应，以5.5%的产率制备了一种19元开笼富勒烯衍生物。在孔口边缘有四个羰基、一个醚氧和一个喹喔啉部分。通过在60℃下与盐酸加热4小时，氯离子可以插入其空腔中。在稍高的反应条件下（90℃，14小时），也实现了氟离子、溴离子和碘离子的包封。获得了包封氯离子和溴离子的衍生物的钠盐的单晶X射线结构，其显示卤化物阴离子位于空腔中心，两个钠离子通过与孔口边缘的氧原子配位连接两个笼。在分离产物中，卤化物包封率是定量的。
