Luminescent Hybrid Materials for Photocatalysis and Sensing

本项目的目的是多功能多孔聚合物的制备和详细表征。这包括金属-有机骨架以及纯有机多孔聚合物，例如共轭微孔聚合物。由于它们的高表面积和高孔体积，这些材料允许良好的可及性和高密度的官能团。作为功能基团，不同的金属配合物和荧光团将被研究，这将被应用在两个不同的领域。作为第一个应用，这些材料将被用作光化学反应的多相催化剂。通常，这些反应需要两个官能团，即催化活性中心和光敏剂。光敏剂显示出比活性中心高得多的吸收，从而为催化过程提供所需的能量。到目前为止，光敏剂仅被均匀地溶解在反应混合物中使用，因此在反应后需要额外的纯化步骤。在这个项目中，第一次，催化活性中心和光敏剂将被纳入一个多孔框架。第二个应用是多孔聚合物，用于同时检测各种气体。现有技术的传感器通常提供高灵敏度，但是由于交叉灵敏度而遭受对错误信号的敏感性，因为它们被开发用于检测单个分析物。同样，在项目的这一部分，不同的功能基团，例如荧光团将被纳入一个单一的多孔网络。这将允许同时检测几种分析物。结合不同官能团的传感器响应将允许灵敏和更有选择性的检测。电子转移过程以及反应机理的理解对于这两个主要目标都非常重要。因此，这些过程将通过不同的光谱和时间分辨方法进行研究，并将与材料的结构特性相关。收到的发现和信息将有助于更好地了解多相催化剂和多功能传感器。因此，合理设计新的，更有效的材料将是可能的。

The aim of this project is the preparation and detailed characterization of multi-functionalized porous polymers. This includes metal-organic frameworks as well as purely organic porous polymers such as conjugated microporous polymers. Due to their high surface areas and high pore volumes, these materials allows for a good accessibility and high densities of functional groups. As functional groups, different metal complexes and fluorophores will be investigated, which will be applied in two different areas. As a first application, these materials will be used as heterogeneous catalysts for photochemical reactions. Generally, these reactions require two functional groups, i.e. the catalytically active center and a photosensitizer. The photosensitizer shows a much higher absorption than the active center and thus provides the required energy for the catalytical process. So far, the photosensitizer has only ever been used homogeneously dissolved in the reaction mixture, thus requiring an additional purification step after the reaction. In this project, for the first time, both the catalytically active center and the photosensitizer will be incorporated into one porous framework. Hence a completely heterogeneous catalyst will be obtained.The second application consists of porous polymers for the simultaneous detection of various gases. State of the art sensors usually offer high sensitivities, but suffer from susceptibility to false signals due to cross sensitivities, as they are developed for the detection of a single analyte. Again, in this part of the project, different functional groups, e.g. fluorophores will be incorporated into a single porous network. This will allow for a simultaneous detection of several analytes. Combining the sensor responses of different functional groups will allow for a sensitive and much more selective detection.The understanding of the electron transfer processes as well as the reaction mechanisms is of great importance for both main objectives. Thus, these processes will be investigated by different spectroscopic and time-resolved methods and will be correlated to the structural properties of the materials. The findings and information received will contribute to a better understanding of heterogeneous catalysts and multi-functional sensors. Hence a rational design of new, more efficient materials will be possible.