几种含多环芳烃的水溶性冠醚分子键合与组装行为研究

One of the important goals of supramolecular chemistry is to create the synthetic receptors that have both a high affinity and a high selectivity for the binding of guests in water. In this project, we will design and synthesize a series of water- soluble multisulfonated anthracene/pyrene-bridged bis-dibenzo-24-crown-8/bis- dibenzo-30-crown-10 compounds, the water-soluble cryptands comprised of multi- sulfonated bis-anthracene/bis-pyrene-bridged bis-dibenzo-24-crown-8/bis-dibenzo- 30-crown-10, the multisulfonated binaphthyl-26-crown-8/binaphthyl-32- crown-10, bis-binaphthyl-28- crown-8/binaphthyl-34-crown-10, and the stiff-stilbene derivatives substituted by two viologen groups. Based on the characteristics of the plentiful pi electron and sereval negative charges in these crown ethrrs and cryptands, we will investigate the binding ability, selectivity, binding mode between these crown ethrrs/cryptands and organic ammoniums, pyridiniums, amino acids, polypeptides, saccharides in water by spectrometry, electrochemistry, the isothermal titration calorimetry, and so on. Furthermore, we will prepare some pseudorotaxanes/polypseudorotaxanes through the complexation of these crown ethrrs/cryptands with the stiff-stilbene derivatives, investigate the relative movement of the components in assemblies as well as their macroscopic property, reveal the thermodynamic origin of their molecular recognition, as well as the rule between the structure of host molecules and their molecules selectivity. These investigations might open a new door for the study and application of crown ether chemistry.

设计合成在水中对客体分子既具有高键合能力又具有高选择性的人工受体是超分子化学的重要研究方向。该项目拟设计合成一系列水溶性蒽基/芘基荧光团桥联的多磺酸取代双苯并24冠8/30冠10、多磺酸取代双蒽基/双芘基-双苯并24冠8/30冠10穴醚、多磺酸取代联萘并26冠8/32冠10和双联萘并28冠8/34冠10、以及双紫精取代的刚性二苯乙烯衍生物，利用冠醚/穴醚中多环芳烃固有的丰富pi电子以及多个负电荷的特征，通过谱学、电化学、量热等手段研究这些冠醚和穴醚在水溶液中对有机胺盐、吡啶盐以及氨基酸、多肽、核苷酸、糖类等生物小分子的键合能力、选择性、键合模式，进而与双紫精取代的刚性二苯乙烯作用构建(聚)准轮烷类超分子组装体，研究光刺激下组装体内各组件的相对运动以及所表现出的宏观性质，探索主体对客体分子选择键合的热力学起源，阐明主体结构与识别客体分子能力之间的关系，为冠醚的研究和开发利用提供新的路线。

冠醚作为第一代超分子大环化合物，被广泛用于构筑分子机器、分子器件、金属离子传感器和智能材料等，而水溶性的大环主体与发光客体分子通过非共价相互作用构筑具有特定功能的组装体是近年来超分子化学领域的研究热点之一。在国家自然科学基金面上项目的资助下，我们开展了“几种含多环芳烃的水溶性冠醚分子键合与组装行为研究”。该项目设计合成了单苯并联二萘26-冠-8、蒽基桥联双苯并24-冠-8、氰基苯乙烯桥联双24-冠-8以及偶氮苯桥联的二苯并-24-冠-8等含多环芳烃以及碳碳、氮氮双键的双冠醚，研究了这些冠醚受体与不同发色团的二级铵盐、手性联二萘、二芳基乙烯衍生物以及胆固醇修饰的二级铵盐等客体分子形成超分子体系的键合模式、组装体形貌、手性传递机理，实现了多刺激响应的发光开关功能。进而利用水溶性的柱芳烃、环糊精和葫芦脲构建了具有宽光谱多色发光包括白光发射的水相人工光捕获体系和具有室温磷光的水溶性超分子体系，实现了高效的能量转移效率和天线效应，这些工作不仅在光驱动手性开关以及信息存储等方面潜在的应用前景，而且为模拟自然界光合成提供了潜在的途径。以上研究取得了一系列重要的阶段性成果，研究成果在Adv. Optical Mater.、Chem. Commun.、Org. Biomol. Chem.等一些刊物上发表论文8篇，短期内他引63次。