Synthesis and spectroscopic characterization of high-spin nitrenes

高自旋有机分子是基础研究的基础，具有潜在的应用价值，可以作为合成有机磁体的基石。由于它们的不成对电子，这些分子通常是高度反应性的，需要通过使用基质隔离技术或使用大块取代基作为“内部基质”来实现动力学稳定。亚硝基烯是三重态分子，在EPR中具有大的单重态-三重态分裂和非常大的零场分裂参数。尽管它们具有很高的反应活性，但它们可以被认为是合成磁性模型化合物的理想基石。因此，在Ruhr-Universität波鸿和俄罗斯科学院的合作中，我们计划系统地探索聚亚胺的光谱和化学性质。一些前驱体将被合成和研究的基质分离光谱。主要的光谱工具将是EPR光谱，但红外和紫外-可见光谱以及最先进的ab-initio和DFT计算也将被使用。通过结合两个实验室的专业知识，我们有信心能够合成和表征这些难以捉摸的反应中间体，并详细了解它们的电子结构。

High-spin organic molecules are of fundamental interest for basic research with potential applications as building blocks for the synthesis of organic magnets. Due to their unpaired electrons these molecules are in general highly reactive and require kinetic stabilization either by using the matrix isolation technique or by using bulky substituents as “internal matrix”. Nitrenes are triplet molecules with large singlet-triplet splittings and very large zero-field splitting parameters in the EPR. Despite their high reactivity they can thus be regarded as ideal building blocks for the synthe-sis of magnetic model compounds. In a cooperation between the Ruhr-Universität Bochum and the Russian Academy of Sciences we therefore plan to systematically explore the spectroscopic and chemical properties of polynitrenes. A number of precursors will be synthesized and investi-gated by matrix isolation spectroscopy. The main spectroscopic tool will be EPR spectroscopy, but IR and UV-vis spectroscopy as well as state of the art ab-initio and DFT calculations will also be used. By combining the expertise from the two labo-ratories we are confident to be able to synthesize and characterize these elusive reac-tive intermediates and gain detailed insight into their electronic structure.