文献类型：期刊文献

英文题名：2Ch-2N square and hexagon interactions: a combined crystallographic data analysis and computational study

作者：Lu, Yunxiang[1,2];Li, Wenxia[1,2];Yang, Weiwei[1,2];Zhu, Zhengdan[3];Xu, Zhijian[3];Liu, Honglai[1,2]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Dept Chem, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Inst Mat Med, Drug Discovery & Design Ctr, Shanghai 201203, Peoples R China

年份：2019

卷号：21

期号：38

起止页码：21568

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;EI(收录号：20201708552686);WOS:【SCI-EXPANDED(收录号:WOS:000488835000034)】；

基金：This work was supported by the National Natural Science Foundation of China (21473054 and 91834301).

语种：英文

外文关键词：Binding energy - Substitution reactions - Scaffolds

摘要：In recent years, chalcogen bonding (ChB), a typical sigma-hole interaction, has shown great potential as a bottom-up design approach for specific applications. According to our survey of the Cambridge Structural Database (CSD), a large number of crystal structures containing 2Ch-2N square and hexagon interaction motifs were extracted. On the basis of the CSD search results, the 2Ch-2N square interactions in the dimers of 2,1,3-benzochalcogenadiazole 1 and 2,1,3-pyridochalcogenadiazole 2, together with 2Ch-2N hexagon interactions in the dimers of chalcogenazolo-pyridine 3 and triazolo-chalcogenadiazole 4, were firstly studied. Then, substituent effects on these peculiar interactions were thoroughly examined by introducing a diversity of small, non-aromatic substituents at the 4,7-positions of the 1S scaffold and various aryl substituents at the 2-position of the 3Te scaffold. Our calculations showed that the major contribution to the attraction of such bidentate ChB interactions is electrostatics, while the orbital term also plays an important role. Some strong electron-withdrawing substituents, such as NO2, CN, and CF3, tend to enhance square ChB interactions, while C6F5 and CF3 substituents with a strong electron-withdrawing ability strengthen hexagon ChB interactions. Particularly, a good linear correlation has been established between the binding energies of the dimers under study and both the surface electrostatic potential (ESP) maxima for the Ch sigma-holes and the minimum surface ESP of the N atoms, which provides reasonable models to evaluate these interactions. The results reported in this work will provide design guidance for the applications of 2Ch-2N cyclic motifs in materials science and biochemistry.