Chemical and Spectroscopic Investigation of Nitrenium Ions and Related Species

这个奖项是在有机动力学项目中颁发的，是在马里兰大学丹尼尔·法尔维教授的研究支持下颁发的。这项研究涉及氮离子的化学和光谱研究，氮离子是由n -氨基吡啶盐光化学产生的。两个特定的领域将被解决：(1)氮离子的溶液反应性，特别是与亲核试剂；(2)定义控制其单重态-三重态能量间隙的氮离子的结构特征。前者将采用激光闪光光解和光热束偏转量热法探测，后者将采用低温电子顺磁共振波谱法探测。实验研究将辅以半经验和从头计算。氮离子作为有机反应中的活性中间体，尚未得到很好的研究。对控制它们的单线态-三重态能隙的结构特征的研究，将为新磁性材料的设计提供基础信息。此外，研究氮离子对亲核试剂的反应性将有助于揭示它们在DNA损伤和致癌作用中的作用。

This award is made in the Organic Dynamics Program in the support of the research of Prof. Daniel Falvey at the University of Maryland. The research deals with chemical and spectroscopic studies of nitrenium ions, photochemically generated from N-aminopyridinium salts. Two specific areas will be addressed: (1) the solution reactivity of nitrenium ions, particularly with nucleophiles, and (2) defining the structural features of nitrenium ions which control their singlet-triplet energy gaps. The former will be probed by laser flash photolysis and photothermal beam deflection calorimetry and the latter by low temperature electron paramagnetic resonance spectroscopy. Experimental studies will be complemented by semi-empirical and ab initio calculations. Nitrenium ions, as reactive intermediates in organic reactions, have not been well explored. This study of the structural features which control their singlet-triplet energy gaps, will provide fundamental information which will aid in the design of new magnetic materials. Additionally, the study of the reactivity of nitrenium ions towards nucleophiles will shed light on their role in DNA damage and carcinogenesis.