CAREER: Valence Orbital Control in f-Block Complexes

通过这一职业奖，化学部化学合成计划支持佐治亚理工学院Henry S.La Pierre教授的研究，以建立稀土原子具有异常高或低电荷的化合物的合成化学、磁性和光谱。驱动原子核年龄的化学元素来自元素周期表的底部，包括榄系元素和镧系元素。这些元素加在一起被称为f元素。今天，f元素及其化学络合物在能源生产、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、硬磁铁和电子产品等领域的大规模技术发展。尽管多年来人们对f元素进行了深入的研究，但对它们成键的基本化学控制是不完整的。在这方面，能够扩大我们利用f元素的不寻常成键特征的能力的知识是非常重要的。这些物种是基于镧系元素的新技术在量子信息科学和量子材料等应用中的基础。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。他们还将参与一项面向社区的外联计划，以增加经济困难和代表性不足的少数族裔学生获得科学职业的机会。该项目建立了合成化学和配体设计，以控制和利用稀土络合物中的多组态和混合价基态。这些目标要求开发合成方法来调节稀土元素中可接近的氧化态：特别是扩大可接近的四价和二价稀土络合物的范围。这种合成方法与物理表征和反应性研究相结合，提供了对稀土材料中如何出现多构型和混价现象以及这些现象如何影响热力学、动力学和磁性的基本见解。特别是用X射线吸收光谱、电子顺磁共振和磁探针对四价氧化态稳定的电子基础和导致三价和二价镧系元素混合基态的配位场考虑进行了解释。这些基本物理和化学性质的确定可能会使以f元素为基础的重要技术进步成为可能。这项支持还建立了一个教育和外展计划，以提高亚特兰大大都会区经济困难和代表性不足的少数族裔社区对科学职业的认识和获得机会。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.