Synthesis and spectroscopic characterization of high-spin nitrenes

高自旋有机分子在基础研究中具有重要意义，可作为有机磁体合成的基础材料。由于它们的未成对电子，这些分子通常是高度反应性的，并且需要通过使用基质分离技术或通过使用大体积取代基作为“内部基质”来进行动力学稳定。氮烯是三重态分子，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。尽管它们的反应活性很高，但它们可以被认为是合成磁性模型化合物的理想结构单元。 因此，在鲁尔大学波鸿和俄罗斯科学院之间的合作中，我们计划系统地探索聚氮烯的光谱和化学性质。一些前体将被合成并通过基质隔离光谱进行研究。主要的光谱工具将是EPR光谱，但也将使用IR和UV-vis光谱以及最先进的从头算和DFT计算。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，并获得详细的电子结构。

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.