Chemical and Spectroscopic Studies of Organic Radical Cations

有机自由基阳离子的化学和光谱研究

• 批准号: 9714850
• 负责人: Heinz Roth
• 金额: $ 31.35万
• 依托单位: Rutgers University New Brunswick
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-12-01 至 2003-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9714850&HistoricalAwards=false
• 关键词: Chemical; Spectroscopic; Studies; Organic; Radical

Professor Heinz D. Roth, of the Department of Chemistry at Rutgers, the State University of New Jersey, carries out chemical and spectroscopic studies of organic radical cations with the support of the Organic and Macromolecular Chemistry Program. Organic radical cations are generated by photo-induced electron transfer and by chemical oxidation in a range of media, including fluid solutions, frozen glasses, and solid supports (zeolites). Spectroscopic techniques, including optical spectroscopy, electron paramagnetic resonance, and chemically induced dynamic nuclear polarization, permit the study of the structures of these radical cations. Through a combination of experimental and theoretical techniques, Professor Roth explores the regiochemistry of radical cation reactions, focusing on ring strain, extent of conjugation, and steric hindrance as determinants of regioselectivity. Also explored are issues relating to the reactions of triplet radical pairs, including biradical formation, generation of biradicals or triplet states from `vertical` radical cations, formation of perpendicular triplet states, and generation of extended biradicals by coupling of triplet ion pairs. Many chemical reactions proceed via a sequence of chemical steps, each producing a reactive intermediate species which undergoes further reaction, ultimately leading to the final reaction product. The intermediates in chemical reactions often display unusual chemical and structural features, and often bear a positive charge (`cations`) or negative charge or a lone electron (`radicals`). With the support of the Organic and Macromolecular Chemistry Program, Professor Heinz D. Roth, of the Department of Chemistry at Rutgers, the State University of New Jersey, studies the formation, structure, and reactivity of reactive intermediates containing both a positive charge and an unpaired electron. Through the application of a variety of physical and chemical techniques, complemented by calculational studies, Professor Roth elucidates the chemical nature of these `radical cations,` contributing to our fundamental knowledge of how chemical reactions occur.

海因茨教授D.罗格斯大学化学系的罗斯说， 新泽西的州立大学，进行化学和光谱 有机自由基阳离子的研究与支持的有机和 高分子化学计划。 产生有机自由基阳离子 通过光诱导电子转移和通过化学氧化， 介质，包括流体溶液、冷冻玻璃和固体支持物 （沸石）。 光谱学技术，包括光学光谱学， 电子顺磁共振和化学诱导动态核 极化，允许研究这些自由基的结构， 阳离子。 通过实验和理论的结合 技术，罗斯教授探讨了自由基阳离子的区域化学 反应，重点是环应变，共轭程度和空间位阻 阻碍作为区域选择性的决定因素。 还探讨了一些问题 与三重态自由基对的反应有关，包括双自由基 从“垂直”形成、产生双自由基或三重态 自由基阳离子，垂直三重态的形成，以及 通过三重态离子对的偶联产生扩展的双自由基。 许多化学反应通过一系列化学步骤进行， 产生反应性中间体物质，其进一步经历 反应，最终得到最终的反应产物。 的 化学反应中的中间体通常显示出不寻常的化学性质， 结构特征，并经常带有正电荷（“阳离子”）或 负电荷或孤电子（“自由基”）。 的支持下 有机与高分子化学项目，海因茨教授D。罗斯， 罗格斯大学化学系，新泽西州州立大学 泽西岛，研究的形成，结构和反应活性 含有正电荷和不成对电子的中间体。 通过应用各种物理和化学 技术，辅以计算研究，罗斯教授 阐明了这些“自由基阳离子”的化学性质， 我们对化学反应如何发生的基础知识。