Chemical and Spectroscopic Investigation of Nitrenium Ions and Related Species

该奖项是在有机动力学计划的支持下， 马里兰州大学的丹尼尔·法尔维教授的研究。的 研究涉及化学和光谱研究， 氮烯 离子，从N-氨基吡啶鎓盐光化学产生。两 具体领域将得到解决：（1）溶液的反应性 氮鎓离子，特别是与亲核试剂，和（2）定义 氮鎓离子控制其单重态-三重态的结构特征 能源缺口。 前者将通过激光闪光光解进行探测， 光热束偏转量热法和后者由低 温度电子顺磁共振谱实验 研究将补充半经验和从头算 计算。 氮离子作为有机反应中的活性中间体， 被很好地探索。本研究的结构特征，控制 它们的单重态-三重态能隙， 这将有助于设计新的磁性材料。 此外，本发明还 研究氮离子对亲核试剂的反应性将 揭示了它们在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.