Construction of Metallo-nano Architecture Possessing Cooperative Functions

我们设计和合成了多种具有协同功能的金属纳米分子系统，这些系统对外界刺激作出反应。其基本结构有伪大环、伪大环和c型金属骨架。例如，由含联吡啶的三足体与Fe（II）反应得到的假隐体对碱金属离子的识别表现出正变构和负变构效应。这种新型调节是通过诱导拟合识别控制来实现的。此外，在螺旋伪隐体与铯离子络合后，金属宿主被拉长并以弹簧的形式扭曲。相应的结构变化可以应用于纳米分子机器。我们还制备了一种新的线性低聚肟配体，该配体被定量地和协同地转化为c形的三角配合物。在络合过程中，未观察到单锌和二锌络合物的形成。有趣的是，c形结合位点中心只有一个锌原子被镧系元素和钙定量取代。钙在碱土金属中的选择性极高，可与著名的钙结合剂相媲美。根据这种有效的转金属方法，还制备了一种新的具有铁磁相互作用的Cu，Gd异三核配合物。以杯状[4]芳烃为骨架，合成了一种多反应阴离子受体。阴离子的识别被阳离子作为效应物逐步地、显著地控制。

We have designed and synthesized various metallo-nano molecular systems possessing cooperative functions, which respond to external stimuli. The basic structures are pseudomacrocyclic, pseudomacrobicyclic and C-shaped metallo frameworks. For example, a pseudocryptand obtained from reaction of a tripodand bearing bipyridines with Fe(II) exhibited both positive and negative allosteric effects on recognition of alkali metal ions. This new type of regulation is achieved by control of induced-fit recognition. In addition, upon the complexation of the helical pseudocryptand with cesium ion the metallohost is elongated and twisted in a spring like fashion. The responding structural change may be applied to nano-molecular machines. We have also prepared a novel linear oligooxime ligand, which is quantitatively and cooperatively converted to a C-shaped trizinc complex. During the complexation formation of the mono-and dizinc complexes was not observed. Interestingly, only one zinc atom captured in the center of the C-shaped binding site was replaced quantitatively by lanthanide and calcium. The selectivity of calcium among alkaline earth metals is extremely high and comparable to those of famous calcium binders. A new Cu,Gd heterotririuclear complex, which exhibits ferromagetic interaction, was also prepared according to this effective transmetalation method. A multi-responding anion receptor was synthesized by using a calix[4]arene framework. The anion recognition was controlled stepwise and dramatically by cations as an effector.