CAREER: Valence Orbital Control in f-Block Complexes

职业：f-嵌段配合物中的价轨道控制

• 批准号: 1943452
• 负责人: Henry La Pierre
• 金额: $ 45万
• 依托单位: Georgia Tech Research Corporation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-08-01 至 2025-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1943452&HistoricalAwards=false
• 关键词: CAREER; Valence; Orbital; Control; Block

With this CAREER Award, the Chemical Synthesis Program of the Chemistry Division supports the research of Professor Henry S. La Pierre at the Georgia Institute of Technology to establish the synthetic chemistry, magnetism, and spectroscopy of compounds in which lanthanide atoms have unusual high or low charge. The chemical elements that drive the nuclear age are from the bottom of the periodic table and include the actinide and lanthanide elements. Together these are known as the f-elements. Today, the f-elements and their chemical complexes play key roles in energy production, conversion, and use. In addition, these elements are driving large-scale technological developments in areas including lighting, hard magnets, and electronics. While the f-elements have been intensively studied over the years, fundamental chemical control of their bonding is incomplete. In this respect knowledge that can expand our ability to utilize unusual bonding features of the f-elements is very important. These species are a foundation, for new lanthanide-based technologies in applications including quantum information science and quantum materials. The graduate and undergraduate students who carry out this research will be trained in a wide range of physical and synthetic techniques. They will also participate in an outreach program to the community to increase access to scientific careers among economically disadvantaged and underrepresented minority students.This project establishes the synthetic chemistry and ligand design to control and exploit multi-configurational and mixed-valence ground states in lanthanide complexes. These goals require the development of synthetic methodology to regulate the accessible oxidation states in the lanthanides: in particular, to expand the scope of accessible tetravalent and divalent lanthanide complexes. This synthetic methodology, in conjunction with physical characterization and reactivity studies, provides fundamental insight into how multi-configurational and mixed-valence phenomena emerge in lanthanide materials and how these phenomena influence thermodynamics, kinetics, and magnetism. In particular, X-ray absorption spectroscopy, electron paramagnetic resonance, and magnetic probes are employed to elucidate the electronic basis of the stabilization of the tetravalent oxidation state and the ligand field considerations which lead to mixed-valent ground states in tri- and divalent lanthanides. Determination of these fundamental physical and chemical properties may enable important f-element-based technological advances. This support also establishes an educational and outreach program to increase awareness of and access to scientific careers among economically disadvantaged and underrepresented minority communities the Atlanta Metro area.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.

有了这个职业奖，化学系的化学合成计划支持教授亨利S。拉皮埃尔在格鲁吉亚理工学院建立合成化学，磁性和光谱的化合物，其中镧系元素原子具有不寻常的高或低电荷。驱动核时代的化学元素是周期表的底部，包括锕系元素和镧系元素。这些元素统称为f元素。今天，氟元素及其化学复合物在能源生产、转换和使用中发挥着关键作用。此外，这些元素正在推动照明、硬磁和电子等领域的大规模技术发展。虽然多年来对f元素进行了深入的研究，但对其键合的基本化学控制还不完整。在这方面的知识，可以扩大我们的能力，利用不寻常的键特征的f-元素是非常重要的。 这些物种是量子信息科学和量子材料等应用中新的镧系元素技术的基础。进行这项研究的研究生和本科生将接受广泛的物理和合成技术培训。他们还将参加一个社区外展计划，以增加经济困难和代表性不足的少数民族学生的科学事业。该项目建立了合成化学和配体设计，以控制和利用镧系元素络合物中的多构型和混合价基态。这些目标需要开发合成方法来调节镧系元素中可接近的氧化态：特别是，扩大可接近的四价和二价镧系元素络合物的范围。这种合成方法，结合物理表征和反应性研究，提供了基本的洞察如何多构型和混合价现象出现在镧系元素材料，以及这些现象如何影响热力学，动力学和磁性。特别是，X-射线吸收光谱，电子顺磁共振，和磁探针来阐明稳定的四价氧化态和配位场的考虑，导致混合价基态的三价和二价镧系元素的电子基础。这些基本物理和化学性质的确定可能使重要的f-元素为基础的技术进步。这项支持还建立了一个教育和推广计划，以提高认识和获得科学事业之间的经济弱势和代表性不足的少数民族社区亚特兰大Metro area.This奖项反映了NSF的法定使命，并已被认为是值得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的支持。

项目成果

Spectroscopic and electrochemical characterization of a Pr 4+ imidophosphorane complex and the redox chemistry of Nd 3+ and Dy 3+ complexes

Pr 4 亚氨基正膦络合物的光谱和电化学表征以及 Nd 3 和 Dy 3 络合物的氧化还原化学

• DOI: 10.1039/d2dt00758d
• 发表时间: 2022
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Rice, Natalie T.;Popov, Ivan A.;Carlson, Rebecca K.;Greer, Samuel M.;Boggiano, Andrew C.;Stein, Benjamin W.;Bacsa, John;Batista, Enrique R.;Yang, Ping;La Pierre, Henry S.
• 通讯作者: La Pierre, Henry S.

Chalcogen-atom abstraction reactions of a Di-iron imidophosphorane complex

• DOI: 10.1039/d1cc02195h
• 发表时间: 2021-06-07
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Aguirre Quintana, Luis M.;Yang, Yan;La Pierre, Henry S.
• 通讯作者: La Pierre, Henry S.