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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具有协同功能的金属-纳米分子体系，这些体系对外界刺激有响应。基本结构为假大环、假大双环和C形金属骨架。例如，从三脚架轴承联吡啶与Fe（II）的反应得到的假穴配体表现出积极和消极的识别碱金属离子的变构效应。这种新型的调节是通过控制诱导配合识别来实现的。此外，在与铯离子络合的螺旋假穴配体的金属主机被拉长和扭曲的弹簧一样的方式。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，它是定量和合作转化为C形三锌配合物。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，只有一个锌原子被捕获在中心的C-形结合位点定量取代镧系元素和钙。钙在碱土金属中的选择性极高，与著名的钙粘合剂相当。利用这种有效的金属转移方法，合成了一种新的具有铁磁相互作用的Cu，Gd异三核配合物。以杯[4]芳烃为骨架，合成了一种多响应阴离子受体。阴离子识别是逐步控制和显着的阳离子作为效应。