基于杯芳烃主体的分子自组装研究进展

分子自组装是超分子化学最重要的研究内容之一. 杯芳烃作为继冠醚、环糊精之后的第三代人工合成受体分子已在分子自组装研究方面取得了重要进展并显示了广泛的应用前景. 主要综述杯芳烃衍生物通过氢键、金属诱导配位、π-π作用、疏水作用等非共价键弱相互作用力在溶液状态、固态和界面的分子自组装方面的研究进展.     

二萘嵌苯桥联双二苯并24冠8的合成及其与富勒烯二级铵盐的组装行为

通过端基为伯胺的臂式二苯并24冠8与苝四甲酸二酐衍生物的缩合反应合成了二萘嵌苯桥联的双冠醚主体.利用核磁、荧光等手段研究了其与富勒烯二级铵盐客体形成准轮烷的组装行为.结果表明,24冠8大环可以键合二级铵盐客体,形成轮上有二萘嵌苯和轴上有富勒烯的准轮烷,KPF6和18冠6的加入可以调控准轮烷的解离和形成,并伴随着荧光强度的改变.     

钾离子调控的1,5-萘基桥联双冠醚的

报道了萘基桥联双苯并15-冠-5的合成, 研究了K^＋调控的双冠醚自组装过程以及伴随的独特荧光行为. 这种发光行为不仅可以模拟一个荧光"off-on-off"开关和一个荧光"on-off-on"开关, 而且其组装模式和功能上类似于酶的二聚化过程.     

18-冠-6修饰苝酰亚胺衍生物的合成及离子识别行为

合成了一种18-冠-6修饰的苝酰亚胺衍生物(1), 研究了其作为主体对金属离子与阴离子的选择性识别行为. 结果表明, 主体1对Ba²⁺离子具有一定的选择性响应, 并可以通过Ba²⁺调控主体1的堆积行为; 主体1还对F^-离子有选择性响应, F^-与苝酰亚胺单元之间发生了阴离子-π相互作用.     

基于24-冠-8大环化合物构筑的人工分子器件和分子机器

简要阐述了分子器件和分子机器的相关概念,按照调控方式分类综述了基于24冠8的准轮烷、轮烷和索烃大环化合物构筑的分子器件和分子机器等在超分子领域的研究进展并对研究前景作了展望.     

基于喹啉和三唑环的开链冠醚对金属离子的选择传感

本文通过Click化学反应合成了一种含喹啉基和三唑基的开链冠醚, 考察和比较了主体化合物对镉等金属离子的荧光传感和选择性键合行为, 并通过荧光和核磁等手段研究了溶剂对其荧光传感的影响.     

Molecular design of crown ethers .18.~1 Cationextractability and selectivities of selena-13- to 14-crown-4

Three selena-crown-4 derivatives have been prepared and their cation binding abilities and selectivities with alkali and heavy metal ions have been evaluated by solvent extraction of aqueous metal picrates to show the highest Ag extractability for novel benzo-selena-14-crown-4 (2,3-benzo-7,12-diselena-1, 4-dioxacyclotetradecane-2-ene) over any other crown ethers.     

一对含有苯甲醛基修饰的杯芳烃异构体的晶体结构以及它们与铽离子配位的光物理性质

Two calix[4]arene isomers with benzaldehyde moieties, i.e., 5,11,17,23-tetra-tert-butyl-25,27-bis[2-(o-formyl-phenoxy)ethoxy]-26,28-dihydroxycalix[4]arene (3) and 5,11,17,23-tetra-tert-butyl-25,27-bis[2-(p-formylphenoxy)-ethoxy]-26,28-dihydroxycalix[4]arene (4), were synthesized according to a newly designed route in high yields, and their crystal structures have been determined by X-ray crystallographic study. The photophysical behavior on complexation of calix[4]arene derivatives 3 and 4 with terbium(Ⅲ) nitrate was investigated in anhydrous acetonitrile at 25℃ by UV-Vis and fluorescence spectroscopies. The crystallographic structure of 3 indicated that the eight oxygen atoms formed a preorganized ionophoric cavity due to intramolecular π-π stacking, which could encapsulate lanthanide ions tightly. In sharp contrast, the compound 4 formed a linear array by intermolecular π-π stacking, hence the oxygen atoms of pendant arms could not coordinate with metal ions, giving a poor binding ability to Tb^3 . The absorption spectra of 3 with Tb^3 showed clearly a new broad intense absorption at 385nm. Interestingly, the narrow emission line spectrum has also been observed for compound 3 with Tb^3 , and the results obtained were discussed from the viewpoint of energy transfer mechanism between host structures and the properties of lanthanide ions.     

冠醚的分子设计及其识别性质研究进展

综述了冠醚化学研究的最新进展：包括低对称冠醚、臂式冠醚、双冠醚等的分 子设计和离子键合、离子识别的热力学起源和分子组装的研究进展。