【作者】 王倩；

【导师】 刘育；

【作者基本信息】 南开大学 ， 有机化学， 2013， 博士

【摘要】 超分子化学是一门处于材料化学、近代化学以及生命科学交汇点的新型学科,在催化、能源、材料、生物以及医药等诸多领域有着广泛的应用。其中大环主体分子环糊精、葫芦脲和杯芳烃都是超分子化学非常重要的研究方向。在本文的工作中,我们选择了以上三种超分子主体作为研究对象,利用各自的特点,研究了它们在分子识别、超分子组装体的构筑以及超分子光化学反应中的一些应用。论文的主要内容和创新点如下：1.简要介绍了超分子化学的概况,并对环糊精、葫芦脲以及杯芳烃在分子识别、分子组装所取得的重要成果和最新进展以及超分子光化学反应的研究进展进行了简要介绍。2.设计合成萘酚修饰的β-环糊精以及金刚烷-紫精双功能基团客体分子,利用环糊精对金刚烷的强键合以及葫芦脲能够通过主体稳定的电荷转移相互作用对萘酚和紫精进行稳定的共包结,成功构筑了一个基于两种大环主体的超分子聚合物。我们利用一维核磁、二维ROESY、二维扩散排序核磁共振谱、质谱、动态光散射以及多种电镜表征手段研究了此超分子聚合物的形成和形貌。并利用超分子组装体中可逆的主客体相互作用,通过加入竞争客体1-金刚烷胺,研究了此超分子聚合物的形成/解聚过程。3.将萘以两种不同方式修饰到γ-CD上得到两种不同的环糊精衍生物,并将其引用到蒽酸的光二聚反应中来调控反应结果。我们通过荧光光谱以及光反应数据证明了环糊精上沿的修饰基团萘在296nm激发后,能够与空腔中的AC分子之间发生FRET作用,不仅增强AC的光反应效率还能使反应有较高的立体选择性。另外,由于FRET的作用,当将主客体比例减小到0.3时,上述较高的立体选择性依然保持,因此,这又是一个催化超分子光不对称合成的例子。4.研究了在天然γ-环糊精及修饰γ-环糊精存在下,2-蒽酸以及2,6-二蒽酸的光二聚反应结果对激发波长的依赖性,并通过改变反应溶剂、反应温度等外部条件来进一步调节反应的产物分布以及手性产物的ee值。据我们所知,这是首例通过改变激发波长来调节光反应产物化学选择性及立体选择性的报道。5.合成了三个带有不同烷基链的二茂铁类客体分子,并在pH=2.0以及pH=7.0两个条件下,通过核磁光谱以及微量热滴定实验研究了磺化杯[4]芳烃以及硫桥磺化杯[4]芳烃与三个客体的键合模式、键合稳定常数以及热力学起源。更多还原

【Abstract】 Supramolecular chemistry is one of the important research aspects in chemistry, which is widely used in the fields of catalysis, energy, material, biology, medicine, and so on. Among macrocyclic host molecules, cyclodextrins, cucurbituril, and calixarenes have become some main focuses in supramolecular chemistry. In the thesis, we chose cyclodextrins, cucurbiturils, and calixarenes as the basic research objects to study their recongnition behavior, to construct nanostructural supramolecular polymer as well as manipulate photochirogeneis, which are summarized as follows:1. The general aspect of supramolecular chemistry was described briefly. The new progress and important achievements on supramolecular chiral photochemistry, molecular recognition and assembly of cyclodextrins, cucurbiturils, and calixarenes were reviewed.2. A novel supramolecular ternary polymer mediated by macrocyclic molecules cucurbit[8]uril and cyclodextrin was successfully constructed, based on the cucurbit[8]uril-stabilized charge-transfer interaction and cyclodextrin-adamantane host-guest interaction, which was well characterized by various methods, including diffusion ordered1H NMR spectroscopy, dynamic light scattering, gel permeation chromatography, scanning electron microscopy, atomic force microscopy as well as transmission electron microscopy. In addition, benefiting from the non-covalent nature of supramolecular interactions, we can control the assembly/disassembly of the present supramolecular polymer by adding a competitive guest, such as1-adamantaneamine to the system.3. γ-Cyclodextrin (CD) derivatives with a naphthalene moiety anchored to one or two of the glucose units of the CD were synthesized in order to investigate the effects of flexible and rigid capping upon complexation, as well as Forster resonance energy transfer and photochirogenic behavior of anthracenecarboxylate (AC) moieties. UV-vis, circular dichroism and fluorescence spectral studies revealed that two AC molecules are simultaneously included into the modified γ-CD cavity to form a right-handed screw and also that the naphthalene cap efficiently transfers the singlet energy to AC included in the CD cavity via the FRET mechanism. Interestingly, FRET excitation further enhanced the chemical and optical yields of anti-HH dimer up to36%and35%ee, for which the highly efficient FRET sensitization within the CD cavity, minimizing the "contamination" from the achiral "outside" photoreaction, is responsible. FRET sensitization also enabled us to achieve the catalytic photocyclodimerization of AC with a sub-equivalent amount of chiral supramolecular host.4. By studying the photoreaction of AC in altering excitation wavelengths, we have demonstrated for the first time that the excitation wavelength can be used as a unique, convenient, yet powerful tool for manipulating the relative yield and ee of chiral photoproducts obtained in supramolecular photochirogenesis, circumventing the inherent limitations of ground-state thermodynamics.5. Three guests bearing the ferrocene backbone and varying length of alkyl chains were synthesized. The binding modes, inclusion abilities and thermodynamics between the three guests with p-sulfonatocalix[4]arene (SC4A) and p-sulfonato thiacalix[4]arene (STC4A) at pH2.0and pH7.0were studied, mainly employing the methods of1H NMR,2D ROESY and isothermal titration calorimetry. The results showed that both SC4A and STC4A could form stable complexes with the ferrocene-based guests at pH7.0with binding constants from2.7×104to1.6×105while the binding constants were a little smaller at pH2.0. Furthermore, the binding modes between hosts and guests were quite different at different pH value.更多还原