Electronic and Chemical Properties of Nitrenium Ions and Ion Diradicals

通过这一奖项，有机和高分子化学项目支持马里兰州马里兰大学学院公园化学系丹尼尔·E·福尔维教授的工作。这项研究将包括对镍离子和离子双自由基的电子和化学性质的研究，并探索合成聚苯胺的新的光化学途径。在这些研究中，将采用实验和理论相结合的方法，生成一系列短命的阳离子中间体，包括氮离子、碳离子和氧离子，并阐明它们的电子性质。PI实验室最近的计算研究预测，这些中间体中的适当取代将导致具有高自旋三重基态的结构。这些研究将结合使用激光闪光光解、化学、陷阱实验、低温EPR光谱、SQUID磁测量和电子结构计算，其长期目标是识别持久或稳定的高自旋三重态物种。此外，还将探索一条合成聚苯胺的新的光化学路线。这些研究旨在合成稳定的高自旋分子，将有助于设计具有有用的磁性和电性的有机材料。发展一种具有良好特性的光化学方法来合成聚苯胺，将有助于制造利用这种聚合物的纳米和微米级电子器件。参与这个项目的研究生和本科生将在有机合成、聚合物化学、计算化学和光化学方面获得宝贵的经验。

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.