CAREER: Valence Orbital Control in f-Block Complexes

通过这个职业奖，化学部门的化学合成项目支持乔治亚理工学院的Henry S. La Pierre教授的研究，以建立合成化学、磁性和光谱的化合物，其中镧系原子具有不寻常的高或低电荷。驱动核时代的化学元素位于元素周期表的底部，包括锕系元素和镧系元素。这些元素一起被称为f元素。今天，f元素及其化学配合物在能源生产、转化和利用中起着关键作用。此外，这些元素正在推动照明、硬磁铁和电子等领域的大规模技术发展。虽然多年来人们对f元素进行了深入的研究，但对它们成键的基本化学控制尚不完整。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基于镧系元素的新技术的基础。从事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方面的培训。他们还将参加一个面向社区的推广项目，以增加经济上处于不利地位和代表性不足的少数民族学生从事科学事业的机会。本项目建立了合成化学和配体设计，以控制和利用镧系化合物中的多构型和混合价基态。这些目标需要发展合成方法来调节镧系元素的可接近氧化态：特别是扩大可接近的四价和二价镧系元素配合物的范围。这种合成方法，结合物理表征和反应性研究，提供了对多构型和混合价现象如何在镧系材料中出现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，利用x射线吸收光谱、电子顺磁共振和磁探针来阐明四价氧化态稳定的电子基础，以及导致三价和二价镧系元素混合基态的配体场考虑。确定这些基本的物理和化学性质可能会使重要的基于f元素的技术进步成为可能。这项支持还建立了一个教育和推广计划，以提高亚特兰大地铁地区经济弱势和代表性不足的少数民族社区对科学事业的认识和机会。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值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.