Photocatalytic Redox-neutral Aryl-diazene Synthesis via Dinitrogen Fixation

我们的目标是建立一种通过单电子还原活化分子氮的方法，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改性金刚石表面的特殊性质上，在激发时，由于电子的负电子亲和力，它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氮素反应，在质子化后产生反应性的N2H自由基。我们努力通过与芳香烃反应来捕获这些活性中间体。在氧化还原中性过程中，二氮被插入到一个C-H键中，得到的双氮烯分子可以作为各种重要的有机氨基化合物的平台化学物质。由于钻石具有5.47 eV的很大带隙，目前只能通过紫外线照射才能从钻石中光生出溶剂化电子。在这个项目中，我们的目标是使用可见光。这需要对钻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形成杂化金刚石材料等几种策略来引入所需的带隙内状态。反应堆的设计将进行量身定制，以便能够使用两相系统产生溶剂化电子，并通过与适当的芳烃反应将其提取到有机相中。

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.