MOE Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University , Beijing 100084, China.
CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Science, Beijing National Laboratory for Molecular Sciences , Beijing 100191, China.
J Org Chem. 2018 Feb 2;83(3):1502-1509. doi: 10.1021/acs.joc.7b03136. Epub 2018 Jan 23.
The synthesis, conformational structure, electronic property, and anion complexation of novel coronarenes were systematically studied. A number of corona[4]arene[2]tetrazines that contain different combinations of nitrogen atoms with O, S, SO, and CH as bridging units were synthesized conveniently by means of a fragment coupling strategy based on efficient nucleophilic aromatic substitution reaction of easily available aromatic dinucleophiles and 3,6-dichlorotetrazine. The resulting macrocycles adopt crownlike conformational structures with the nitrogen bridge(s) forming conjugation with carbonyl and the other heteroatom linkages with tetrazine. CV and DPV measurements showed that the tetrazine-bearing coronarenes were electron deficient with reduction potentials ranging from -896 to -960 mV. Owing mainly to noncovalent anion-π attractive interactions, N,O-corona[4]arene[2]tetrazine formed complexes with anions of varied geometries and shapes yielding diverse assembled structures in the solid state.
我们系统地研究了新型冠醚的合成、构象结构、电子性质和阴离子络合。通过基于易得芳基双亲核试剂与 3,6-二氯四嗪之间的高效亲核芳香取代反应的片段偶联策略，方便地合成了一系列含有不同氮原子与 O、S、SO 和 CH 作为桥联单元的冠[4]芳烃[2]四嗪。所得大环采用冠状构象结构，其中氮桥（s）与羰基形成共轭，而其他杂原子键与四嗪形成共轭。CV 和 DPV 测量表明，含四嗪的冠醚具有电子缺陷，还原电位范围为-896 至-960 mV。主要由于非共价阴离子-π 吸引相互作用，N,O-冠[4]芳烃[2]四嗪与具有不同几何形状和形状的阴离子形成配合物，在固态中生成不同的组装结构。
