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Construction of Metallo-nano Architecture Possessing Cooperative Functions

具有协同功能的金属纳米结构的构建

基本信息

批准号：
15350076
负责人：
NABESHIMA Tatsuya
金额：
$ 9.92万
依托单位：
University of Tsukuba
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

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.

我们设计并合成了各种对外界刺激具有协同功能的金属-纳米分子体系。其基本结构为拟大环、拟大双环和C形金属骨架。例如，含有联吡啶的三脚体与Fe(II)反应得到的假石膏对碱金属离子的识别既有正负变构效应，也有正负变构效应。这种新型的调节是通过对诱导匹配识别的控制来实现的。此外，在螺旋假石膏和铯离子的络合作用下，金属基质以弹簧的方式被拉长和扭曲。相应的结构变化可应用于纳米分子机器。我们还制备了一种新型的线性低聚肟配体，它可以定量地、协同地转化为C型三锌络合物。在络合过程中，没有观察到单锌和双锌络合物的形成。有趣的是，只有一个捕获在C型结合位点中心的锌原子被稀土和钙定量取代。碱土金属中钙的选择性极高，可与著名的钙粘结剂相媲美。用这种有效的易金属化方法还制备了一种新的具有铁磁相互作用的铜、Gd异三核配合物。以杯[4]芳烃为骨架合成了一种多响应型阴离子受体。阴离子的识别是由阳离子作为效应器逐步而显著地控制的。