Expanding the Scope of Group 13 Chemistry with Redox-Active Ligands

在化学系化学合成计划的资助下，加州大学戴维斯分校化学系的路易丝·伯本教授将探索铝和相关元素在化学反应中转移电子的基本能力。该项目的动机是，在许多重要的有用的化学过程中，涉及到或来自金属物种的电子转移。虽然能够做到这一点的金属是众所周知的，但它们通常是稀有和昂贵的。为了获得更经济的电子转移物种，本项目将重点放在铝这一廉价而丰富的金属上。这项研究提出了新的铝化合物的设计，这种化合物可以传递电子，并可能在大规模能量存储和许多工业过程中应用。与加州大学的ACS项目SEED、加州大学戴维斯分校的NSF REU项目和第一代大学生项目的合作将分别为经济困难的高中生和本科生提供研究指导和项目经验。这个项目集中在第13组化学的两个领域的发展。首先，我们将制备含氧化还原活性配体的有机铝化合物，并研究其基于配体的给体-受体性质。一个重点是发展结构-功能关系，以便分子中的氧化还原过程可以通过调节分子结构来控制。在第二个领域，将发展正方形平面族13元素金属芳香族化合物的反应化学。该项目这一部分的目标是探索金属-配体多键和金属-芳香族反应化学。在这个项目中，Berben团队将使用无机合成技术来获得用于研究的新材料和分子，我们将使用电化学方法、单晶X射线衍射、核磁共振和电子顺磁共振(核磁共振和电子顺磁共振)、近红外、红外和X射线吸收光谱对这些新化合物进行表征。EPR和X射线吸收光谱将在合作努力中进行。拟议工作的好处和成果包括扩大在化学和材料应用中利用铝的能力，以及培训熟练的劳动力使用铝和其他第13族元素。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 funding from the Chemical Synthesis Program in the Chemistry Division, Professor Louise Berben in the Department of Chemistry at the University of California – Davis will explore the fundamental ability of aluminum and related elements to transfer electrons during chemical reactions. The project is motivated by the fact that in many important useful chemical processes involve electron transfer to or from a metal species. While metals that are capable of doing this are well known, they are often rare and expensive. In order to obtain more economical electron transfer species this project focuses on aluminum, which is an inexpensive and plentiful metal. The research puts forward designs of new aluminum compounds that can transfer electrons and may lead to applications in large scale energy storage and in many industrial processes. Collaborations with ACS Project SEED, the UC-Davis NSF REU program, and First-Gen College student programs at the University of California will provide research mentoring and project experience to economically disadvantaged high school students, and undergraduates, respectively. This project centers on the development of two areas of group 13 chemistry. In the first, organoaluminum compounds containing redox-active ligands will be prepared and the ligand-based donor-acceptor properties will be investigated. A focus is on developing structure-function relationships so that redox processes in the molecules can be controlled by modulation of molecular structure. In the second area, the reaction chemistry of square planar group 13 element metallo-aromatic compounds will be developed. The goal of this portion of the project is to explore metal-ligand multiple bonding and metallo-aromatic reaction chemistry. In pursuing this project, the Berben group will employ inorganic synthesis techniques to obtain new materials and molecules for study, and we will characterize these new compounds using electrochemical methods, single crystal X-ray diffraction, nuclear magnetic and electron paramagnetic resonance (NMR and EPR), near infra-red, infra-red, and X-ray absorption spectroscopy. The EPR and Xray absorption spectroscopies will be performed in collaborative efforts. Benefits and outcomes of the proposed work include an expanded ability to utilize aluminum in chemistry and materials applications, and training of a skilled workforce to work with aluminum and other group 13 elements.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.