Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (7): 2848-2860.DOI: 10.6023/cjoc202102012 Previous Articles     Next Articles

分子间卤键控制的氢键芳香酰胺折叠体组装

许艳艳a, 刘传志a,b, 王辉a, 张丹维a,*(), 黎占亭a,*()   

  1. a 复旦大学化学系 上海市分子催化和功能材料重点实验室 上海 200438
    b 商丘师范学院化学系 河南商丘 476000
  • 收稿日期:2021-02-02 修回日期:2021-03-05 发布日期:2021-03-25
  • 通讯作者: 张丹维, 黎占亭
  • 基金资助:
    国家自然科学基金(21772026); 国家自然科学基金(21890732); 国家自然科学基金(21890730)

Intermolecular Halogen Bonding-Controlled Self-Assembly of Hydrogen Bonded Aromatic Amide Foldamers

Yanyan Xua, Chuanzhi Liua,b, Hui Wanga, Danwei Zhanga(), Zhanting Lia()   

  1. a Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Shanghai 200438
    b Department of Chemistry, Shangqiu Normal University, Shangqiu, Henan 476000
  • Received:2021-02-02 Revised:2021-03-05 Published:2021-03-25
  • Contact: Danwei Zhang, Zhanting Li
  • Supported by:
    National Natural Science Foundation of China(21772026); National Natural Science Foundation of China(21890732); National Natural Science Foundation of China(21890730)

Six intramolecular hydrogen bonding-induced aromatic amide foldamers have been prepared through the formation of the hydrazone bond in the last step. The compounds are attached with one trifluoroiodobenzene as halogen donor and one pyridine ring as halogen bonding acceptor. Intermolecular I…N halogen bond formed by the above two units and other kinds of halogen bonds are designed to modulate the stacking of the compounds in the solid state. It is revealed that intermolecular halogen bonding can induce the molecules to form extended zigzag arrays, dimeric macrocycles or supramolecular helices. The formation of the dimeric macrocycles is favored when the halogen bond donor and acceptor are located in a parallel manner. Longer tetrameric and pentameric sequences give rise to more curved, crescent conformations, with the two halogen bonding donor and acceptor on the ends to form a large angle. For two compounds, polar methanol or water prevents the formation of the intermolecular end-to-end halogen bonding by forming I…O halogen bonding. The pentameric compound is connected by methanol to form supramolecular single helices. For another pentameric compound, strong I…O=C halogen bonding is found to induce the backbone to self-assemble into supramolecular single helices. The single helices further stack to afford supramolecular double helix arrays.

Key words: halogen bond, hydrogen bond, foldamer, helix, crystal engineering, macrocycle, aromatic amide, hydrazone