Synthesis, Complexation Properties, and Hierarchical Organisation of Maktrozyclic Assemblies of Perylene Bisimide Dyes

基于我们在第一个资助期开发的合成全环联二亚胺大环(二聚体至二十二聚体)的合成方法，第二个资助期侧重于利用这些大环作为超分子主体来络合功能客体分子(芳烃、染料、富勒烯、催化剂)，以及大环在溶液中和表面上的自组装成更大的超分子组件。在超分子主体的家族中，我们最感兴趣的是二酰亚胺环番，它们的空腔大小和形状可以定制，以适应更大的芳香客体分子的络合。特别有趣的客体分子是生物碱(传感器应用)和催化剂。前者将在大环主体的环芳二亚胺中诱导CD效应，后者由于利用了手性环番环境而提供对映选择性。作为较大的主体分子，我们将特别采用三聚体大环和金属超分子四面体。通过合成平面大环(即没有大团的大环)，我们打算通过自组装获得管状聚集体。这些管子的内部将充满用于光伏应用的富含电子的客体分子。为了控制这些分子的自组装过程，我们将进一步装备它们与金属离子配位的外受体，以使二维和三维自组装成为高度多孔的结构，这些结构可能是非晶态的，也可能是晶态的。这些结构将扩展目前已知的金属有机骨架(MOF)领域的结构。

Based on the synthetic methods that we developed in the first funding period for the synthesis of perylene bisimide macrocycles (dimers up to nonamers) the second funding period is focused on the utilization of such macrocycles as supramolecular hosts for the complexation of functional guest molecules (aromatics, dyes, fullerenes, catalysts) as well as the self-assembly of macrocycles in solution and on surfaces into larger supramolecular assemblies. Within the family of supramolecular hosts we are most interested in perylene bisimide cyclophanes whose cavity size and shape can be tailored for the complexation of larger aromatic guest molecules. Particularly interesting guest molecules are alkaloids (sensor applications) and catalysts. The former shall induce CD effects in the perylene bisimides of the macrocyclic hosts, the latter shall - just opposite - afford enantioselectivity due to the utilization of a chiral cyclophane environment. As larger host molecules we will employ in particular trimeric macrocycles and metallosupramolecular tetrahedra. By the synthesis of planar macrocycles (i.e. without bulky groups) we intend to obtain tubular aggregates by self-assembly. The interior of these tubes will be filled with electron rich guest molecules for photovoltaic applications. To control self-assembly processes of these molecules we will equip them furthermore with exoreceptors for the coordination of metal ions to enable two- and three-dimensional self-assembly into highly porous structures which may be amorphous or crystalline. These structures will expand the currently known ones in the area of metal-organic frameworks (MOFs).