Synthesis and spectroscopic characterization of high-spin nitrenes

高自旋氮烯的合成及光谱表征

• 批准号: 86403934
• 负责人: Professor Dr. Wolfram Sander
• 金额: --
• 依托单位: Organische Chemie II - Physikalisch-Organische Chemie (AG Sander)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2008
• 资助国家: 德国
• 起止时间: 2007-12-31 至 2011-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/86403934?language=en
• 关键词: Synthesis; spectroscopic; characterization; spin; nitrenes

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.

高自旋有机分子对于基础研究具有重要意义，具有作为有机磁体合成的构建模块的潜在应用，由于它们的不成对电子，这些分子通常具有高反应性，并且需要通过使用基质隔离技术或通过动力学稳定。使用庞大的取代基作为“内部基质”，氮烯是三线态分子，在 EPR 中具有大的单线态-三线态分裂和非常大的零场分裂参数，因此它们可以被视为理想的。因此，在波鸿鲁尔大学和俄罗斯科学院的合作中，我们计划系统地探索聚氮烯的光谱和化学性质，并研究多种前体。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从头算和 DFT 计算也将是。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。

项目成果

EPR studies on branched high-spin arylnitrenes.

支化高自旋芳基氮烯的 EPR 研究

• DOI: 10.1002/cphc.201200200
• 发表时间: 2012
• 期刊: Chemphyschem : a European journal of chemical physics and physical chemistry
• 作者: Chapyshev; S. V.;Korchagin; D. V.;Budyka; M. F.;Gavrishova; T. N.;Neuhaus; P.;S;er; W.
• 通讯作者: W.

Matrix isolation and IR spectroscopic characterization of 3,5‐difluoropyridyl‐2,4,6‐trinitrene

3,5â二氟吡啶â2,4,6â三硝基的基质分离和红外光谱表征

• DOI: 10.1002/poc.1943
• 发表时间: 2012
• 期刊: Journal of Physical Organic Chemistry
• 影响因子: 1.8
• 作者: Finke; C.;Grote; D.;Seidel; R. W.;Chapyshev; S. V.;S;er; W.
• 通讯作者: W.

High-spin intermediates of the photolysis of 2,4,6-triazido-3-chloro-5-fluoropyridine

2,4,6-三叠氮-3-氯-5-氟吡啶光解的高自旋中间体

• DOI: 10.3762/bjoc.9.83
• 发表时间: 2013
• 期刊: Beilstein Journal of Organic Chemistry
• 影响因子: 2.7
• 作者: Chapyshev; S. V.;Korchagin; D. V.;Neuhaus; P.;S;er; W.
• 通讯作者: W.