离子型刚性有机金属化合物自组装形成的超分子软物质

This proposal aims to a systematic investigation on structurally rigid small-molecular-weight ionic metal-organic compounds that can self-assemble in aqueous solutions into a variety of supramolecular soft matter, such as lyotropic chromonic liquid crystals, hydrogels and supramolecular polymeric nanomaterials. This type of non-traditional amphiphiles are essentially ion pairs consisting of a rigid and hydrophobic metal-organic ion and a small but highly hydrophilic counter-ion which is selected from the lyotropic Hofmeister series. The molecular structures and self-assembling mechanism are thus different from those of the traditional surfactants/detergents. The special building blocks include but are not limited to the following categories: a) Cationic and b) Anionic non-traditional amphiphiles; c) Double complex salts; and d) Zwitterionic inner salts. Novel allenylidene metal coordination is the representative innovative structural moiety in the molecular design that reinforces the rigidity of the complexes while stabilizing the low-valence metal center. This proposal also aims to in situ study the macroscopic dynamic responsive behavior of the supramolecular soft matter towards a variety of controllable micro-environmental factors, such as temperature, mechanical force (pressure, shearing and stretching), pH, and redox reagents. The goal of this proposed research is to fully understand the rules governing the assembling processes and structure-property relationship between the structurally rigid metal-organic compounds and the resulted supramolecular soft matter. The successful commission of this proposal will finally lead to advanced functional materials based on novel metal-containing supramolecular soft nanostructures.

此项目旨在系统研究基于离子型刚性小分子金属有机化合物的凝胶、溶致液晶和超分子聚合物纳米结构等软物质材料。这类软物质的形成和自组织不是来自传统的带有烷基长链的表面活性剂，而是来自非传统双亲分子，即疏水离子型配合物和亲水抗衡离子的离子对。分子设计包括了以新型亚丙二烯基金属化合物为代表的多种刚性离子型有机金属化合物：（1）阳离子型非传统双亲分子；（2）阴离子型非传统双亲分子；（3）双配合物盐；（4）分子内盐型刚性配合物。着力于新的结构基元的设计。探索从刚性小分子有机金属配合物出发得到超分子软物质的可控合成与组装规律。项目还将采用多手段的原位测量技术表征有机金属配位超分子软物质对温度、机械力（压力、剪切力、拉伸力）、pH、氧化还原剂等可控环境因素的宏观动态响应行为。以期最终实现有机金属超分子软物质的定向合成与功能化。

此项目旨在系统研究基于离子型刚性小分子金属有机化合物的凝胶、溶致液晶和超分子聚合物纳米结构等软物质材料。以分子聚集软物质研究为本项目的研究方向，设计合成了几类新型的水溶性或者双亲性金属有机分子化合物并分别研究了这种水溶性或双亲性带来的新性质：二（亚丙二烯基）金（I）化合物在水溶液中可以自组织形成独特的chromonic（溶色）液晶； 联二亚胺二（亚丙二烯基）铂（II）化合物具有阴离子调节的溶解性和自组装性质；二亚胺（亚丙二烯基）铼（I）化合物，当阴离子为氯离子时，化合物具有同时溶解于水相和脂相的双亲性；亚丙二烯基引入到三齿环钯金属配合物，在无限长的Pd-Pd作用下表现出多重响应的磷光性质。在以上考察金属间弱相互作用导向的自组装研究的基础上，利用可折叠构型的二齿芳基炔配体，构建双核钳形环金属Pd(II)化合物，实现对Pd⋯Pd相互作用的调控，表现出高效率红色磷光发射，可以作为构建溶液中高效磷光Pd(II)化合物的原型；还利用Au-Au(Cu)相互作用，将阳离子型卡宾金（I）配合物与相应的金（I）或者铜（I）阴离子形成双盐型聚集体，并考察了磷光性质与金属间相互作用及环境刺激响应之间的构效关系；进一步从理论角度，利用理论与计算化学手段考察了亲金属、色散力等弱相互作用对光致发光的影响。此外，另外在项目执行过程中，还设计有一类水溶性磺酸钠金（I）炔化合物在水溶液中自组装不明显，但是在DMSO溶液中显示出全新的新性质：光照活化的磷光。在此基础上在保护磷光三重态及其应用领域取得较多的原创性研究成果，在探究现象机理的基础上已经将这一新现象拓展至相关应用领域。