Construction of Self-assembled Hybridized Materials Having Intelligent Functions

迄今为止报道的大多数组装金属配合物是由适当的双齿有机间隔物和三角形、四面体和八面体金属模板组合而成的，其中金属离子用作连接部分。但是，由于金属离子不能作为反应位点，形成的纳米孔不能根据分子的大小或形状而变化，这是缺点。这些问题将通过使用非共价相互作用位点（如氢键和疏水键）修饰的金属配合物来解决。在此之前，我们报道了一些双核金属配合物与双胍和双脲配合物之间的三氢键连接。本课题旨在构建一种新型的纳米多孔过渡金属配合物，该配合物仅具有三氢键和疏水相互作用，并建立一种新的制备方法。在这个项目中，我们设计并制作了一、二、三维的配合框架，如螺旋、砖墙、阶梯、蜂窝、方网、拼花、菱形等更复杂的连接化合物。利用这些方法构建具有纳米孔框架的配位聚合物，由于其潜在的功能，如大小选择性分子吸收，形状选择性催化和离子交换，因此引起了人们的极大兴趣。在这里，我们成功地制备了一种新型的纳米多孔金属配合物，这种配合物是由带有非共价相互作用基团（如氢键和疏水基团）的金属配合物构成的。

Most of assembled metal complexes reported hitherto are constructed with a combination of appropriate bidentate organic spacers and trigonal, tetrahedral, and octahedral metal templates, in which the metal ions are used as joining parts. However, these are disadvantage from the viewpoint that the metal ions are not available as the reactive site and the formed nano-pores cannot change according to the molecular sizes or shapes. These problems will be settled by the use of the metal complexes modified with non-covalent interaction sites such as hydrogen bonding and hydrophobic ones. Previously, we reported some dinuclear metal complexes linked with a triple hydrogen-bond between the biguanidato and biuretato complexes. The objective of this research project is to construct novel nano-porous transition metal complexes assembled with only the triple-hydrogen bonding and hydrophobic interactions and to establish a new methodology for the preparation methods. In this project, we designed and prepared one-, two-, and three-dimensional coordination frameworks, such as helical, brick wall, ladder, honeycomb, square grid, parquet, diamondoid and more complicate connective compounds. The construction of coordination polymers with nano-porous frameworks using these methodologies are of great interest due to their potential functionalities such as size-selective molecular absorption, shape-selective catalysis, and ion-exchange. Here, we succeeded in preparation of a novel nano-porous metal complex that has been constructed from the metal complexes bearing non-covalent interaction groups such as hydrogen bonding and hydrophobic ones.