SusChEM: Expanding Reductive Chemistry with the Rare Earth Metals

SusChEM：用稀土金属扩展还原化学

• 批准号: 1265396
• 负责人: William Evans
• 金额: $ 56.1万
• 依托单位: University of California-Irvine
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-05-01 至 2016-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1265396&HistoricalAwards=false
• 关键词: SusChEM; Expanding; Reductive; Chemistry; Rare

With this award from the Chemical Synthesis (SYN) Program of the Chemistry Division,, Professor William J. Evans of the Department of Chemistry of the University of California, Irvine, and his students will utilize the unique properties of the rare earth metals, i.e., the lanthanides, yttrium, and scandium, to explore new aspects of redox chemistry, i.e., the reduction/oxidation reactions that constitute one of the two most general classes of chemical reactions. Because the rare earth metals represent extremes in the periodic table due to their unusual physical properties, they are an excellent set of elements for expanding the limits of this fundamental reaction type. The chemistry of the (N2)3- and (NO)2- radicals, new reduced forms of diatomic molecules of biological, industrial, and atmospheric significance that were discovered via the rare earths, will be examined. The reasons why (N2)3- is so effective in forming single molecule magnets with the highest blocking temperatures known to date will be pursued. The reactivity and physical properties of seven new rare earth oxidation states, the divalent cations of Y, Ho, Er, Tb, Pr, Gd, and Lu, discovered while exploring the reductive reactions that generated the anionic radicals above, will also be examined. In addition, the recent discovery of reductive photochemistry for rare earth complexes, found in a reaction powerful enough to reduce dinitrogen to the anion (N=N)2-, will be studied.Because redox reactions are central to so many processes in life and are critical to processes important in global sustainability such as solar water splitting and dinitrogen reduction, this research can have a broad impact on science and technology. More specifically, the reductive rare earth metal based discovery of the (N2)3- and (NO)2- radical anions has implications in biological, industrial, and atmospheric dinitrogen and nitrogen oxide chemistry. The (N2)3- radical also has demonstrated a new approach to the synthesis of single molecule magnets, entities that could have far-reaching implications in energy utilization and data storage. In general, this project allows the exploration of an under-developed set of elements, the rare earth metals, which are a valuable national resource with many technological applications, while providing training to students in f element chemistry that is essential to addressing issues associated with radioactive waste disposal while training the next generation of students in this field.

凭借化学部化学合成（SYN）计划的这一奖项，加州大学欧文分校化学系的William J. Evans教授和他的学生将利用稀土金属的独特性质，即，镧系元素、钇和钪，以探索氧化还原化学的新方面，即，还原/氧化反应是两种最常见的化学反应之一。 由于稀土金属具有不寻常的物理性质，因此它们代表了元素周期表中的极端元素，因此它们是扩展这种基本反应类型极限的一组优秀元素。 （N2）3-和（NO）2-自由基的化学，通过稀土发现的生物，工业和大气意义的双原子分子的新的还原形式，将被检查。 为什么（N2）3-是如此有效地形成单分子磁体与迄今已知的最高阻断温度的原因将被追究。 还将研究在探索产生上述阴离子自由基的还原反应时发现的Y、Ho、Er、Tb、Pr、Gd和Lu的七种新稀土氧化态的二价阳离子的反应性和物理性质。 此外，还将研究最近发现的稀土络合物的还原性光化学，该络合物的还原性光化学反应的强度足以将二氮还原为阴离子（N=N）2-。由于氧化还原反应是生命中许多过程的核心，并且对于太阳能水分解和二氮还原等全球可持续性的重要过程至关重要，因此该研究将对科学和技术产生广泛的影响。 更具体地，基于还原性稀土金属的（N2）3-和（NO）2-自由基阴离子的发现在生物、工业和大气二氮和氮氧化物化学中具有意义。 （N2）3-自由基还展示了合成单分子磁体的新方法，这些磁体可能对能源利用和数据存储产生深远影响。 总的来说，该项目允许勘探一组开发不足的元素，即稀土金属，这是一种具有许多技术应用的宝贵国家资源，同时为学生提供f元素化学方面的培训，这对解决与放射性废物处置有关的问题至关重要，同时培训该领域的下一代学生。