化学学报 ›› 2022, Vol. 80 ›› Issue (10): 1365-1368.DOI: 10.6023/A22080368 上一篇    下一篇

所属专题: 有机氟化学合集

研究通讯

基于分子间卤键的超分子平面大环自组装

刘传志a, 李芬a, 王静静a, 赵晓璐a, 张婷美a, 黄鑫a, 邬梦丽a, 户志远a, 刘新明a,*(), 黎占亭b,*()   

  1. a 商丘师范学院 化学化工学院 药物绿色合成河南省工程实验室 商丘 476000
    b 复旦大学 化学系 上海市分子催化与功能材料重点实验室 上海 200438
  • 投稿日期:2022-08-30 发布日期:2022-10-08
  • 通讯作者: 刘新明, 黎占亭
  • 基金资助:
    河南省高等学校重点科研项目计划(21A150045); 商丘师范学院博士启动经费(700200); 商丘师范学院博士启动经费(700205)

Self-assembly of Supramolecular Planar Macrocycle Driven by Intermolecular Halogen Bonding

Chuanzhi Liua, Fen Lia, Jingjing Wanga, Xiaolu Zhaoa, Tingmei Zhanga, Xin Huanga, Mengli Wua, Zhiyuan Hua, Xinming Liua(), Zhanting Lib()   

  1. a School of Chemistry and Chemical Engineering, Henan Engineering Laboratory of Green Synthesis for Pharmaceuticals, Shangqiu Normal University, Shangqiu 476000, China
    b Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China
  • Received:2022-08-30 Published:2022-10-08
  • Contact: Xinming Liu, Zhanting Li
  • Supported by:
    Key Scientific Research Projects of Colleges and Universities of Henan Province(21A150045); Start-up Foundation for Scientific Research of Newly Recruited PhD of Shangqiu Normal University(700200); Start-up Foundation for Scientific Research of Newly Recruited PhD of Shangqiu Normal University(700205)

本工作报道了含卤键供体和受体片段的三种芳酰胺分子(化合物1~3)的设计和合成, 并对固相中卤键的不同作用模式进行了探索和分析. 化合物1的晶体数据显示, 由于没有分子内氢键, 组成分子的三个芳环相互扭转一定角度, 并且在分子间交替排列的N···I和O···I卤键的控制下, 组装成了一条线型的超分子组装体. 由于酰胺羰基和两个紧邻的氟原子之间的排斥作用, 化合物2未能形成分子内三中心氢键. 在此基础上, 将三氟碘代苯作为卤键供体片段引入到化合物3中, 并且在折叠体骨架中嵌入了嘧啶单元. 化合物3的晶体数据显示, 基于多组有效的分子内三中心氢键和分子间较强的卤键作用, 双分子间形成了[1+1]的超分子大环. 另外, 由于嘧啶环的引入, 使得该超分子大环接近共平面.

关键词: 卤键, 氢键, 晶体工程, 超分子作用, 双分子大环

The design and synthesis of three kinds of arylamide molecules (compounds 1~3) containing halogen bonding donor and acceptor fragments, and the exploration and analyzation of different action modes of halogen bonding in solid phase were reported. Compounds 1 and 2 contain two tetrafluoroiodobenzene fragments, and compound 1 also contains a halogen receptor fragment—pyridine group. Isobutyl groups are introduced into the molecule to increase its solubility and crystallinity. And a pyrimidine fragment was introduced into compound 3, which has more aromatic rings. The two N atoms of the pyrimidine fragment can theoretically form intramolecular hydrogen bonds with the adjacent amide hydrogen atoms (—C(=O)NH), so that the whole molecule has the properties of hydrogen-bonded arylamide foldamer. Moreover, trifluorobenzene fragments were selected in compound 3 to eliminate the repulsion between excess fluorine atoms and carbonyls. The crystal structures reveal that the three aromatic rings in compound 1 are twisted with each other for there is no intramolecular hydrogen bond, and a supramolecular DNA-like double helix was assembled controlled by intermolecular N···I and O···I halogen bonds arranged alternately. Compound 2 failed to form an intramolecular three-center hydrogen bonding due to the repulsion between the amide carbonyl groups and the two fluorine atoms in close proximity. As expected, in the solid phase of compound 3, an effective three-center hydrogen bond is formed between the terminal trifluoroiodobenzene and the benzene ring attached to it. Moreover, the two N—H bonds connected to the pyrimidine ring also form two effective three-center hydrogen bonds. The difference is that the participants of these two groups of three-center hydrogen bonds include two N atoms in the pyrimidine ring. The four aromatic rings in compound 3 are nearly coplanar driven by these intramolecular three-center hydrogen bonds. Two sets of strong intermolecular (pyridine ring) N···I halogen bonds control the formation of [1+1] bimolecular supramolecular macrocycles with inner diameters of 1.36 nm and 1.07 nm in length and width. Moreover, the supramolecular macrocycle is near-planar due to the introduction of pyrimidine ring.

Key words: halogen bond, hydrogen bond, crystal engineering, supramolecular interaction, bimolecular macrocycle