Organic molecules and materials to promote noble metal-free and coupled light-driven catalysis (A06*)

在这个项目中，将开发用于光驱动催化的有机分子化合物。第二个CATALIGHT资助期的两个关键科学问题是，更丰富的化合物，如有机物，是否可以取代传统用于光催化的贵金属光敏剂或催化剂，以及软物质基质的氧化还原特性是否可以用于耦合氧化和还原反应。该项目旨在通过开发(1)利用热激活延迟荧光(TADF)概念的有机光敏剂，以及(2)氧化还原活性有机化合物，允许氧化和还原反应耦合，并将它们整合到软物质基质中，来回答这两个关键的科学问题。对于(1)具有较长激发态的有机染料和TADF将被研究作为光驱动反应中的光敏剂，以取代稀有的贵金属基光敏剂。它们都将被用作小分子光敏剂，以及通过共价键嵌入光敏剂-催化剂二元组。对于(2)有机氧化还原活性单元，可被可逆地氧化并储存正电荷用于时间解耦的催化过程，将被开发，并入聚合物中，并在(还原)析氢反应中进行研究。然后，它们将与可可逆还原的有机聚合物耦合在软物质基质中，并用于氧化和还原的耦合反应方案。

In this project, organic molecular compounds for light-driven catalysis will be developed. Two of the key scientific questions of the 2nd CATALIGHT funding period are whether more abundant compounds, such as organics, can replace noble metal-based photosensitizers or catalysts, traditionally used in photocatalysis, and whether the redox properties of soft matter matrices can be used to couple oxidative and reductive reactions. This project aims to answer to these two key scientific questions by developing (1) organic photosensitizers making use of the thermally activated delayed fluorescence (TADF) concept, and (2) redox active organic compounds that allow coupling oxidative and reductive reactions, and their incorporation in soft matter matrices. For (1) organic dyes showing relatively long-lived excited states and TADF will be investigated as photosensitizers in light-driven reactions to replace rare noble metal-based photosensitizers. They will both be used as small molecule photosensitizers as well as embedded by covalent linkage into photosensitizers-catalyst dyads. For (2) organic redox-active units that can be reversibly oxidized and store positive charges for temporally decoupled catalytic processes will be developed, incorporated into polymers and investigated in (reductive) hydrogen evolution reactions. They will then be coupled in soft matter matrices with organic polymers that can be reversibly reduced and employed in coupled reaction schemes of oxidation and reduction.