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

本项目主要研究了一类新型两亲性萘嵌苯卟啉给体-受体衍生物的合成、超分子组装和电子物理行为。目标是实现对这些化合物的自组装行为的控制，这对于水中聚集体和膜的光诱导电荷分离是必不可少的。通过调整分子结构实现的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，我们将合成前所未有的bola-两亲物在有条不紊的工具箱的方法，这也允许引入各种官能团。此外，我们将系统地研究所选官能团的影响，这改变了单一两亲物的几何和电子性质，关于组装的超结构和物理特性。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，超分子结构对光物理行为的影响，特别是，聚集体内的光诱导电荷分离将被研究。此外，将小分子纳入超分子结构进行了研究。进一步考虑第二种非共价相互作用，将探索rylenebisimide发色团本身在水性环境中通过氢键基序的稳定性。合成方法将围绕trans-meso取代的卟啉，它将连接到萘嵌苯核心和亲水性外围。为了实现所需的亲水性，将利用带有羧酸基团的树枝状结构。随后，将进行这些系统及其聚集体的彻底的结构和生物物理表征，例如，低温透射电子显微镜（TEM），稳态和时间分辨光谱。

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.