对称二环己基取代六元瓜环与3-吡啶甲酰肼的超分子自组装  

Supramolecular Self-assembly of Symmetric Dicyclohexanocucurbit[6]uril and Nicotinic Hydrazide

作　　者：金艳梅 蒙叶 李远 史建华 邓雷 Jin Yanmei;Meng Ye;Li Yuan;Shi Jianhua;Deng Lei(Guizhou Coal Product Quality Supervision&Inspection Institute,Liupanshui 553001,China;Center for Research and Development of Fine Chemicals,Guizhou University,Guiyang 550025,China)

机构地区：[1]贵州省煤炭产品质量监督检验院,六盘水553001 [2]贵州大学精细化工研究开发中心,贵阳550025

出　　处：《化学学报》2022年第1期44-48,共5页Acta Chimica Sinica

摘　　要：本工作以对称二环己基取代六元瓜环(CyH;Q[6])为主体分子,3-吡啶甲酰肼(NH)为客体分子,利用核磁共振(;H NMR)、等温滴定量热(ITC)、基质辅助激光解吸电离飞行时间质谱(MALDI-TOF)研究客体分子与瓜环在水溶液中形成的物质的量比为1∶1的稳定配合物;用X-射线单晶衍射可以观察到客体分子通过离子-偶极和氢键与瓜环端口羰基氧相互作用,以及基于瓜环外壁正电性与无机阴离子之间形成的配合物,从而形成多维多层次超分子框架的自组装体.Cucurbit[n]uril(Q[n]) is a relatively new supramolecular macrocyclic compound, which has a unique structure comprised of a hydrophobic cavity with intermediate potential, two carbonyl portals with negative potential, and an outer surface with positive potential. Cyclohexyl-substituted Q[n]s have also attracted a lot of attention as the first member of the Q[n] family that can be dissolved in organic solvents and water. In this paper, the interaction modes between the symmetric dicyclohexanocucurbit[6]uril(CyH;Q[6]) as a host and nicotinic hydrazide(NH) as a guest were investigated by nuclear magnetic resonance spectroscopy(;H NMR), isothermal titration calorimetry(ITC), matrix assisted laser desorption ionization time of flight(MALDI-TOF) mass spectrometry, and single-crystal X-ray diffraction. The;H NMR spectrum results showed that the proton peaks shift to the downfield, indicating that NH is located at the portal of CyH;Q[6]. ITC experiment results showed that the binding constant(K;) of NH@CyH;Q[6] is(1.019±0.118)×10;L·mol;, the host-guest binding ratio is 0.954±0.013, and the enthalpy value is ΔH=(-48.21±0.35) kJ·mol;and entropy value TΔS=(-31.04±0.52)k J·mol;. The MALDI-TOF mass spectrum also showed that the molecular ion peak m/z is 1242.4542(theoretical value:1242.1603), which is attributed to [CyH;Q[6]·HNH]+. These experimental results showed that CyH;Q[6] formed a stable 1∶1 exclusion complex with NH in an aqueous solution. In addition, the host CyH;Q[6], ZnCl;and the guest NH were added to HCl aqueous solution, and the complex single-crystal structure was obtained by evaporation and standing. The single-crystal structure of the complex showed that there are ion-dipole interactions and hydrogen bonds between the carbonyl oxygen of CyH;Q[6] and NH, and there are ion-dipole interactions between the outer surface of CyH;Q[6] and [ZnCl;];. These weak interactions are the driving forces of the multi-dimensional and multi-level supramolecular framework formed by the complex.

关 键 词：对称二环己基取代六元瓜环 3-吡啶甲酰肼 配合物 超分子框架 自组装体 

分 类 号：O641.3[理学—物理化学]