Programmed Molecular Self-assembly Utilizing Transition Metals : Synthesis and Function of Nano-scale Molecular Materials

利用过渡金属的程序化分子自组装：纳米级分子材料的合成和功能

基本信息

批准号：
14103014
负责人：
FUJITA Makoto
金额：
$ 72.72万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (S)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2006
项目状态：
已结题

项目摘要

In this project, we have focused on the synthesis and function of nano-scale molecular materials by programmed molecular self-assembly utilizing transition metals. Here we summarize our research results that are divided into the five topics. (1)Self-assembly of endo-functionalized molecular spheres : we succeeded in the formation of a liquid-like fluorous droplet, composed of 24 perfluoroalkyl chains confined in the interior of a 5-nanometer-sized, roughly spherical shell. The structures were spontaneously assembled in solution from 12 palladium ions and 24 bridging ligands. (2)Photo-switchable molecular catenate : We achieved a precise, clean molecular lock that operates by light. Since the inert Pt(II)-py bond is considerably labialized upon UV irradiation, we demonstrated the photo-switchable molecular lock by the one-way catenation of coordination rings. (3)Selective recognition and folding of oligopeptides by self-assembled hosts : We anticipated that the large hydrophobic cavity of self-assembled hosts could replace the protein scaffolds and stabilize the secondary structures of oligopeptides. (4)Unusual chemical reactions within self-assembled hosts : We found that an aqueous self-assembled cage induces highly unusual regioselectivity in the Diels-Alder reactions of anthracene and phthalimide molecules, promoting reaction at a terminal ring. (5)Direct crystallographic observation of unstable transition species within self-assembled hosts : We succeeded in the in situ crystallographic observation of a coordinatively unsaturated metal complex within a self-assembled coordination cage.

在这个项目中，我们通过使用过渡金属的编程分子自组装来关注纳米级分子材料的合成和功能。在这里，我们总结了分为五个主题的研究结果。（1）内部官能化的分子球的自组装：我们成功地形成了液体状的透明液滴，该液滴由24个限制在5纳米大小的，大致的球形壳内部的24个全氟烷基链组成。将结构自发地组装在12个钯离子和24个桥接配体的溶液中。（2）可相关的分子息肉：我们实现了通过光线运行的精确，干净的分子锁。由于在紫外线照射下，惰性pt（ii） - py键显着延迟，因此我们通过单向配位环的单向交流表明了可相关的分子锁。（3）通过自组装宿主对寡肽的选择性识别和折叠：我们预计自组装宿主的大疏水腔可以替代蛋白质支架并稳定寡肽的二级结构。（4）自组装宿主中的异常化学反应：我们发现，水自组装的笼子在蒽和邻苯二甲胺分子的Diels alder反应中诱导高度不寻常的区域选择性，从而促进末端环上的反应。（5）对自组装宿主中不稳定过渡物种的直接晶体学观察：我们在自组装配位笼中对协调不饱和金属配合物的原位晶体学观察成功。