Expanding Reductive Chemistry and Oxidation State Diversity within the Synthetic Chemistry of the Rare-Earth Metals

扩大稀土金属合成化学中的还原化学和氧化态多样性

• 批准号: 1855328
• 负责人: William Evans
• 金额: $ 59.4万
• 依托单位: University of California-Irvine
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-01 至 2022-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1855328&HistoricalAwards=false
• 关键词: Expanding; Reductive; Chemistry; Oxidation; State

Professor William J. Evans at the University of California, Irvine, is supported by the Chemical Synthesis Program of the Chemistry Division at NSF. This research addresses chemical reactions of rare-earth elements. Rare-earth elements have been designated critical national resources due to their many technological applications. They are important in magnetism and quantum computing - technologies that have broad potential applications. The project also pursues applications including the development of the smallest, most efficient, magnets, called single-molecule magnets. In addition, students are trained in the use and applications of strategic resources. A component of the project also involves an outreach program to middle and high schools to expose students to rare earths elements, their applications, and the value of scientific research. The chemistry of praseodymium(II), gadolinium(II), terbium(II), holmium(II), erbium(II), and lutetium(II), is being explored to evaluate the special chemical reactions that can arise from their unexpected 4fn5d1 electron configurations. These electron configurations differ from traditional +2 oxidation states of the lanthanide metals (4fn+1 configurations) and could form the basis for new fundamental types of redox chemistry. The chemistry of the new rare earth ion, yttrium(II) (4d1 configuration) is also being studied for comparison. New series of complexes of these +2 ions are synthesized and their reactivity and magnetic and spectroscopic properties are investigated. As these compounds are photoactive diradicals, they present intriguing new options in synthesis, magnetism, and small molecule activation. Among other applications, the development of quantum bits, or qubits, is being pursued.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

加州大学欧文分校的 William J. Evans 教授得到了 NSF 化学部化学合成项目的支持。这项研究涉及稀土元素的化学反应。 稀土元素由于其许多技术应用而被指定为重要的国家资源。它们在磁性和量子计算等具有广泛潜在应用的技术中非常重要。该项目还寻求应用，包括开发最小、最高效的磁体（称为单分子磁体）。 此外，学生还接受战略资源的使用和应用方面的培训。该项目的一个组成部分还涉及到初中和高中的推广计划，让学生了解稀土元素、稀土元素的应用以及科学研究的价值。 正在探索镨 (II)、钆 (II)、铽 (II)、钬 (II)、铒 (II) 和镥 (II) 的化学性质，以评估其意外的 4fn5d1 可能产生的特殊化学反应电子构型。 这些电子构型不同于镧系金属的传统+2氧化态（4fn+1构型），并且可以构成新的氧化还原化学基本类型的基础。 新稀土离子钇(II)（4d1构型）的化学性质也正在研究中进行比较。 合成了这些 +2 离子的新系列络合物，并研究了它们的反应性以及磁性和光谱特性。由于这些化合物是光活性双自由基，它们在合成、磁性和小分子活化方面提供了有趣的新选择。 在其他应用中，量子位或量子位的开发正在被追求。该奖项反映了 NSF 的法定使命，并且通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

2.2.2-Cryptand as a bidentate ligand in rare-earth metal chemistry

2.2.2-稀土金属化学中作为双齿配体的穴状配体

• DOI: 10.1039/d0qi00746c
• 发表时间: 2020
• 期刊: Inorganic Chemistry Frontiers
• 影响因子: 7
• 作者: Chung, Amanda B.;Huh, Daniel N.;Ziller, Joseph W.;Evans, William J.
• 通讯作者: Evans, William J.

Optimizing Alkali Metal (M) and Chelate (L) Combinations for the Synthesis and Stability of [M(L)][(C 5 H 4 SiMe 3 ) 3 Y] Yttrium(II) Complexes

优化碱金属 (M) 和螯合物 (L) 组合以促进 [M(L)][(C 5 H 4 SiMe 3 ) 3 Y] 钇(II) 配合物的合成和稳定性

• DOI: 10.1021/acs.organomet.1c00379
• 发表时间: 2021
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Moore, William N.;Ziller, Joseph W.;Evans, William J.
• 通讯作者: Evans, William J.

Reductive cleavage of N , N ′-di- tert -butylcarbodiimide generates tert -butylcyanamide ligands, (Me 3 CNCN) − , that bind potassium both end-on and side-on in the same single crystal

N , N α-二叔丁基碳二亚胺的还原裂解生成叔丁基氰酰胺配体 (Me 3 CNCN) α ，该配体在同一单晶中以端接和侧接方式结合钾

• DOI: 10.1107/s205698902000732x
• 发表时间: 2020
• 期刊: Acta Crystallographica Section E Crystallographic Communications
• 作者: Chung, Amanda B.;Ziller, Joseph W.;Evans, William J.
• 通讯作者: Evans, William J.

Evaluating electrochemical accessibility of 4f n 5d 1 and 4f n+1 Ln( ii ) ions in (C 5 H 4 SiMe 3 ) 3 Ln and (C 5 Me 4 H) 3 Ln complexes

评估 (C 5 H 4 SiMe 3 ) 3 Ln 和 (C 5 Me 4 H) 3 Ln 配合物中 4f n 5d 1 和 4f n 1 Ln( ii ) 离子的电化学可达性

• DOI: 10.1039/d1dt02427b
• 发表时间: 2021
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Trinh, Michael T.;Wedal, Justin C.;Evans, William J.
• 通讯作者: Evans, William J.

A 9.2-GHz clock transition in a Lu(II) molecular spin qubit arising from a 3,467-MHz hyperfine interaction

• DOI: 10.1038/s41557-022-00894-4
• 发表时间: 2022-03-14
• 期刊: NATURE CHEMISTRY
• 影响因子: 21.8
• 作者: Kundu, Krishnendu;White, Jessica R. K.;Hill, Stephen
• 通讯作者: Hill, Stephen