Photocatalytic Redox-neutral Aryl-diazene Synthesis via Dinitrogen Fixation

建立一种单电子还原激活分子二氮的方法，用于与有机芳香族化合物的直接反应。我们提出的方法建立在修饰金刚石表面的特殊性质上，由于其负电子亲和力，在激发时可以将电子驱逐到水溶液中。早期的研究表明，这些溶剂化的电子与二氮发生反应，质子化后产生活性的N2H自由基。我们努力通过与芳烃的反应来捕获这些活性中间体。在氧化还原中性过程中，二氮被插入到C-H键中，产生二氮分子，二氮分子可以作为多种重要有机氨基化合物的平台化学物质。由于金刚石具有5.47 eV的大带隙，因此目前只能通过紫外照射来实现金刚石溶剂化电子的光产生。在这个项目中，我们的目标是使用可见光。这需要对金刚石材料进行广泛的带隙工程。将采用纳米结构、表面功能化和掺杂以及杂化金刚石材料的形成等几种策略来引入所需的带隙内态。反应器的设计将进行调整，使其能够使用两相系统来产生溶剂化电子，并通过与合适的芳烃反应将其提取为有机相。

We aim to establish a method to activate molecular dinitrogen by one electron reduction for the direct reaction with organic aromatic compounds. Our proposed approach builds on the special properties of modified diamond surfaces, which upon excitation can expel electrons into aqueous solutions due to their negative electron affinity. Earlier studies have shown, that these solvated electrons react with dinitrogen yielding, after protonation, the reactive N2H radical. We strive to trap these reactive intermediates by reaction with aromatic hydrocarbons. In a redox neutral process dinitrogen is inserted into a C-H bond giving diazene molecules that can serve as platform chemical for a variety of important organic amino compounds. The photogeneration of solvated electrons from diamond is currently only possible by UV irradiation as a result of the very large bandgap of 5.47 eV. In this project, we aim for the use of visible light. This requires extensive bandgap engineering of the diamond material. Several strategies including nanostructuration, surface functionalization and doping and the formation of hybrid diamond materials will be pursued to introduce the required intra-bandgap states. The reactor design will be tailored to enable the use of a two-phase system for the generation of solvated electrons and their extraction into an organic phase by reaction with suitable arenes.