【作者】 陈钿；

【导师】 房喻；

【作者基本信息】 陕西师范大学 ， 物理化学， 2006， 硕士

【摘要】 自上世纪60年代以来，超分子化学迅速发展，并逐渐成为区别于传统“分子化学”的“分子以上层次的化学”。Lehn将超分子化学定义为分子组装和分子间“键合”的化学。其主要特点是构造子间通过分子间作用力自组装。伴随着这一过程的进行，体系的流变学行为通常会发生变化。若选择合适的构造子并将其作恰当修饰，则有可能通过调节构造子间的超分子作用来调控体系的流变学行为。据此，可以设计制备一系列刺激响应型流体材料和凝胶材料。 在利用超分子作用调节体系的流变学行为研究中，涉及的主要是主客体相互作用。在此过程中，主体分子和客体分子通过形成主客体包结物构筑超分子一维、二维、或者三维网络结构，因此，体系的流变学行为会随之发生变化，甚至产生相变。 环糊精作为主体化合物能与多种有机、无机以及生物分子形成主客体包结物。这种主客体相互作用不仅受客体尺寸、极性和电性等自身因素的影响，而且受体系的温度、pH值、介质极性以及场效应等外界环境的影响。因此，可通过选择客体或调整环境条件等方式来调节这种相互作用。 基于上述思想，本论文设计合成了双主体双客体超分子构造子，并研究了双客体试剂与双主体之间的主客体相互作用，为制备新颖的超分子结构和软物质材料奠定基础。本论文的实验研究主要包括以下三方面的内容： (1)首先合成了四苯酐桥联β-CD。此外，以二茂铁和乙二胺等为原料合成了二茂铁甲醛和双二茂铁甲醛缩乙二胺，经还原后制得了N，N’-双(二茂铁亚甲基)乙二胺。通过红外光谱、~1HNMR谱和元素分析等手段确证了合成化合物的组成和结构。并利用紫外可见吸收光谱、循环伏安、红外光谱和透射电镜等手段研究了桥联β-CD与N，N’-双(二茂铁亚甲基)乙二胺在水溶液中和固态时的主客体相互作用。结果表明桥联β-CD可与带有两个识别基团的有机分子形成具有线性纳米结构的聚集体或纳米管道。 (2)在第一部分工作中，发现N，N’—双(二茂铁亚甲基)乙二胺在水中的溶解性很差。为了提高这类双客体交联剂在水中的溶解性，以二茂铁为原料合成了二茂铁甲醛，利用二茂铁甲醛与丁二胺的缩合反应以及氢化铝锂对缩合产物的还原作用，合成了双客体物理交联剂，再对其进行甲基化得到更多还原

【Abstract】 Since 1960s, supramolecular chemistry has developed rapidly and established itself as one of the most active fields of science. It is a "chemistry beyond the molecule", which is different from traditional "molecule chemistry". Jean-Marie Lehn has defined supramolecular chemistry as the chemistry of molecular assemblies and of the intermolecular bond. The most important feature of supramolecular chemistry is that the building blocks are held together by intermolecular forces and the rheology behavior of the system usually changes during this process. If the building blocks are chose and modified rightly, it is possible to control the rheology properties by tuning the supramolecular interactions between building blocks. Accordingly, design and preparation of a series of novel supramolecular structures and smart soft materials is possible.In the field of supramolecular interactions controllable rheology behavior, host-guest interaction is the main form which has been investigated systematically. During the process, one, two or three dimensional network can be constructed by forming the host-guest complex between the host and guest molecules. Therefore, a change in rheology behavior may be observed and the phase transition may occure eventually.As an important kind of host, cyclodextrin can form stable inclusion complexes with less polar molecules (guests) that fit tightly inside the cyclodextrin cavity. This host-guest interaction is affected not only by guest’s polarity and size but also by the environment of medium such as temperature, pH, polarity and radiative stimulation. Consequently, the interaction between host and guest can be tuned by varing these conditions.Based upon this methodology, bis-host and bis-guest supramolecular building blocks were designed and prepared in the present study. The host-guest interactions between di-host and di-guest blocks have also been studied. The insight obtained from the studies can be useful for the design and preparation of novel supramolecular structures and smart soft materials.First, a β-cyclodextrin dimmer, benzenetetracarboxylic dianhydride briged bis(p-更多还原