Giant Spherical Supramolecules with Internal and External functions

该项目的目的是将迄今分离的具有主体空腔中功能的相当小的超分子聚集体的现有区域与聚集体内外通常没有官能化的大的多壳层金属团簇的区域统一起来。该方法基于预先设计的具有四个或五个对称多烟源配体的有机金属配合物作为构建块，通过多烟源部分与金属阳离子和/或Lewis酸性配位化合物的多重配位来聚集纳米超分子。该合成策略的目标是通过使用官能化的柔性外球配体或van der Waals以及超分子内腔中的配位相互作用来引入特殊的功能。具有大的、定义明确的空腔的超分子将被用作激活小的、否则不稳定的客体分子的反应容器。外球的功能将导致分别模拟纳米粒子和树枝状大分子的特殊性质。此外，超分子通过连接物的连接将导致一类新型的多孔3D材料，它结合了巨型(主客体可)超分子的性质和MOF材料的高应用潜力。这些巨大的超分子将通过单晶X射线衍射达到原子分辨率来确定最先进的结构。

The aim of this project is to unify the so far separate existing area of rather small supramolecular aggregates with functions in the cavity of the host with the area of large multishell metal clusters with usually no functionalities inside and outside of the aggregates. The proposed approach bases on the use of organometallic complexes with pre-designed four- or five-fold symmetric polypnictogen ligands as building blocks for the aggregation of nano-sized supramolecules via multiple coordination of polypnictogen moieties to metal cations and/or Lewis acidic coordination compounds. The synthetic strategy is targeted at introducing special functionalities either by using functionalized flexible outer sphere ligands or van der Waals and coordinative interactions in the inner cavity of the supramolecules. Supramolecules with large well-defined cavities will be used as ‘reaction vessels’ in the activation of small, otherwise unstable guest molecules. The outer-sphere functionalities will lead to special properties mimicking the chemistry of nanoparticles and dendrimers, respectively. Moreover, the linkage of the supramolecules via linkers will lead to a novel class of porous 3D materials that combines the properties of giant (host-/guest-able) supramolecules with the high application potential of MOF materials. These huge supramolecules will be state-of-the-art structurally determined with single-crystal X-ray diffraction reaching atomic resolution.