Synthesis and Characterization of Amphiphilic Donor-Acceptor Architectures Hybrids Based on Rylene-Porphyrin Hybrids: Towards Charge Separation of Supramolecular Aggregates in Water

本项目将研究一类前所未有的两亲性乙烯-卟啉给受体（D-A）衍生物的合成、超分子组装和光物理行为。目标是实现对这些化合物的自组装行为的控制，这对于光诱导水中聚集体和膜的电荷分离是必不可少的。通过调整分子结构在水介质中的组装将产生由疏水相互作用驱动的严格有序的结构。这些前所未有的系统也将作为研究光合作用关键步骤的模型化合物。为了实现这一目标，我们将以一种系统的工具箱方法合成前所未有的bola-两亲体，这也允许引入各种官能团。此外，我们将系统地研究所选择的官能团对上层结构组装和光物理特性的影响，这些官能团改变了单个两亲化合物的几何端电子特性。这些不同的结构可以在水中产生各种可能的超分子排列，如脂质体、胶束和螺旋柱。因此，将研究超分子结构对聚集体光物理行为的影响，特别是光诱导的电荷分离。此外，将研究小分子与超分子结构的结合。进一步考虑包含第二种非共价相互作用，将通过氢键基序探讨乙烯二酰亚胺发色团本身在水环境中的稳定性。合成方法将围绕反中位取代卟啉，它将连接到乙烯核和亲水外围。为了达到所需的亲水性，将利用带有羧酸基团的树突结构。随后，将对这些系统及其聚集体进行全面的结构和光物理表征，例如，使用低温透射电子显微镜（TEM）、稳态和时间分辨光谱学。

In this project, the synthesis, supramolecular assembly and photophysical behavior of a family of unprecedented amphiphilic rylene-porphyrin donor-acceptor (D-A) derivatives will be investigated. The goal is to achieve control over the self-assembly behavior of these compounds, which is essential for photo induced charge separation of aggregates and membranes in water. Assembly in aqueous media achieved through tailoring the molecular structure will give rise to strictly ordered architectures driven by hydrophobic interactions. These unprecedented systems will also act as model compounds for investigating key steps in photosynthesis. To achieve this, we will synthesize unprecedented bola-amphiphiles in a methodical tool-box approach, which also allows for the introduction of a variety of functional groups. Further, we will systematically investigate the influence of the selected functional groups, which change the geometry end electronic properties of the single amphiphile, regarding the assembly of the superstructure and the photophysical characteristics. These distinct architectures can generate a variety of possible supramolecular arrangements in water such as liposomes, micelles, and helical columns. Consequently, the influence of the supramolecular structure on the photophysical behavior, in particular, the photo-induced charge separation within the aggregates will be studied. Moreover, the incorporation of small molecules into the supramolecular structure will be investigated. Taking the inclusion of a second non covalent interaction even further, the stabilization of the rylenebisimide chromophore itself in an aqueous environment through hydrogen-bonding motifs will be explored. The synthetic approach is going to revolve around trans-meso substituted porphyrins, which will be connected to the rylene core and the hydrophilic periphery. To achieve the required hydrophilicity, dendritic structures bearing carboxylic acid groups will be utilized. Subsequently, thorough structural and photophysical characterization of these systems and their aggregates will be carried out, for example, with cryo transmission electron microscopy (TEM), steady-state, and time resolved optical spectroscopy.