Controlled synthesis of functionalized oligomers and polymers: Development of methods for the solid supported synthesis of quinoxalin-based oligomers using 1,2-diketosynthons for their investigation and application in materials science.

喹恶啉酮类和喹恶啉类化合物是合成、生物和材料科学领域的研究热点。除了许多与药物相关的性质外，喹恶啉结构在材料科学领域也得到了广泛的研究。特别是，可以被一个以上的喹恶啉部分描述的化合物由于具有各种电子和结构性质而引起人们的极大兴趣。喹恶啉被用作电荷转移络合物、新型磁性材料、有机半导体的基础、电池电极、存储介质的电极或新型OLED元件和太阳能电池的配位体。还描述了二恶吩嗪的自组装或其纤维的形成以及螺旋结构的形成，这些螺旋结构可用于开发新的功能材料，例如制备光学活性聚合物。该项目的目的是开发能够在固相上形成和衍生化低聚喹恶啉的方法。聚合物载体的使用意在允许取消先前的合成限制，并因此产生新类别的寡聚喹恶啉和后来的多喹恶啉。新开发的方法旨在提供一种方法，通过该方法，可以以受控的方式使用单个喹恶啉模块的灵活组合来形成低聚喹恶啉。这些模块在融入低聚物的方式上有所不同，并且通过使用不同的喹恶啉构建块来产生额外的多样性。为此，将在固体载体上构建四种类型的模块，这些模块将导致四种不同的低聚结构的线性组合。低聚物组成的不同将对低聚物的整体结构、三维形状以及材料性能产生重大影响。均相低聚物的齐聚合成的发现旨在使合成更多的低聚结构变体成为可能，到目前为止，这是完全未知的。因此，将追求低聚物内的不同变化、各个模块之间的金属配位和共价键的形成以及引入额外的连接基。除了低聚物的合成外，在固相上形成的喹恶啉还用于三聚喹恶啉的裂解，这些三聚喹恶啉可以芳构化得到六氮杂甲基萘的衍生物。最后，将所开发的方法用于测试合成到其他表面的可转移性。其目的是展示一种在平面表面上的应用，以便通过单个模块的受控链接来合成聚合物。

Quinoxalinones and quinoxalines are related substance classes whose investigations in synthetic, biological and materials science are of great interest. In addition to numerous pharmaceutically relevant properties, quinoxaline-containing structures are extensively studied in the field of materials science. In particular, compounds which can be described by more than one quinoxaline moiety are of great interest due to various electronic and structural properties. Quinoxalines are investigated as ligands in charge-transfer complexes, new magnetic materials, the basis for organic semiconductors, battery electrodes, electrodes for storage media, or novel OLED components and solar cells. The self-assembly of dichinoxalinophenazines or their fiber formation has also been described as well as the formation of helical structures, which can be used for the development of new functional materials, e.g. for the preparation of optically active polymers. The aim of this project is to develop methods that enable the formation and derivatization of oligo-quinoxalines on solid phases. The use of the polymeric support is intended to permit the abolition of previous synthetic limitations and, as a consequence, the generation of new classes of oligo- and later poly-quinoxalines. The newly developed methods are intended to provide methods by which a flexible combination of individual quinoxaline modules can be used in a controlled manner for the formation of oligo-quinoxalines. The modules differ in the way of their incorporation into the oligomer and additional diversity is generated by the use of different quinoxaline building blocks. For this purpose, four types of modules are to be constructed on the solid support, which lead in linear combination to four different oligomeric structures. The different constitution of the oligomers will have a significant influence on the overall structure of the oligomer, on its three-dimensional shape as well as on the material properties. The findings from the oligomeric syntheses for homogeneous oligomers are intended to enable the synthesis of further oligomeric structural variants, hitherto completely unknown. Thus, diverse variations within the oligomers, metal coordination and covalent bond formation between the individual modules, as well as the introduction of additional linker groups will be pursued. In addition to the synthesis of oligomers, the formation of quinoxalines on the solid phases is to be used for the cleavage of trimeric quinoxalines, which can be aromatized to give hexaazatrinaphthalene derivatives. The developed methods are used in the last step to test the transferability of the syntheses to other surfaces. The aim is to demonstrate an application on planar surfaces in order to allow syntheses of polymers by controlled linkage of single modules.