Electronic and Chemical Properties of Nitrenium Ions and Ion Diradicals

有了这个奖项，有机和高分子化学计划支持教授丹尼尔E。Falvey博士说，他是马里兰州学院公园市马里兰州大学化学系的教授。 本研究将探讨氮鎓离子及离子双自由基的电子及化学性质，并探讨合成聚苯胺的新光化学途径。实验和理论将被用于这些研究中，其中一系列短寿命的阳离子中间体，包括氮离子，碳离子，和oxenium离子，将产生和阐明其电子性质。PI实验室最近的计算研究预测，在这些中间体中进行适当的取代将导致具有高自旋三重基态的结构。 激光闪光光解，化学，捕获实验，低温EPR光谱，SQUID磁强计和电子结构计算的组合将在这些调查中使用，其长期目标是识别持久或稳定的高自旋三重态物种。 此外，还将探索一种新的光化学合成聚苯胺的途径，这些研究将有助于设计具有有用的磁性和电子特性的有机材料。 发展一种表征良好的合成聚苯胺的光化学方法将有助于利用这种聚合物制造纳米和微米级电子器件。参与本项目的研究生和本科生将获得有机合成，高分子化学，计算化学和光化学方面的宝贵经验。

With this award, the Organic and Macromolecular Chemistry Program supports the work of Professor Daniel E. Falvey, of the Chemistry Department at University of Maryland, College Park, MD. This research will involve studies of the electronic and chemical properties of nitrenium ions and ion diradicals and investigate new photochemical routes to polyaniline. Both experiment and theory will be used in these studies in which a series of short-lived cationic intermediates, including nitrenium ions, carbenium ions, and oxenium ions, will be generated and their electronic properties elucidated. Recent computational studies in the PI's lab predict that appropriate substitutions in these intermediates will lead to structures that have high-spin triplet ground states. A combination of laser flash photolysis, chemical, trapping experiments, low-temperature EPR spectroscopy, SQUID magnetometry and electronic structure calculations will be employed in these investigations, which have the long term goal of identifying persistent or stable high-spin triplet species. In addition, a new photochemical route to polyaniline will be explored.These studies, directed toward the synthesis of stable high-spin molecules, will aid in the design of organic materials that have useful magnetic and electronic properties. The development of a well characterized photochemical method for synthesizing polyaniline will aid in the fabrication of nano and microscale electronic devices that make use of this polymer. Graduate and undergraduate students involved in this project will gain valuable experience in organic synthesis, polymer chemistry, computational chemistry and photochemistry.