基于分子间卤键的超分子平面大环自组装  

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

作　　者：刘传志 李芬 王静静 赵晓璐 张婷美 黄鑫 邬梦丽 户志远 刘新明[1] 黎占亭 Liu Chuanzhi;Li Fen;Wang Jingjing;Zhao Xiaolu;Zhang Tingmei;Huang Xin;Wu Mengli;Hu Zhiyuan;Liu Xinming;Li Zhanting(School of Chemistry and Chemical Engineering,Henan Engineering Laboratory of Green Synthesis for Pharmaceuticals,Shangqiu Normal University,Shangqiu 476000,China;Department of Chemistry,Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,Fudan University,Shanghai 200438,China)

机构地区：[1]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 [2]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

出　　处：《化学学报》2022年第10期1365-1368,共4页Acta Chimica Sinica

基　　金：河南省高等学校重点科研项目计划(No.21A150045);商丘师范学院博士启动经费(Nos.700200,700205)资助。

摘　　要：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.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 supramolecu

关 键 词：卤键 氢键 晶体工程 超分子作用 双分子大环 

分 类 号：O641.3[理学—物理化学]