Electron Delocalization in Linear Heterotrimetallic Compounds

在化学系化学合成项目的支持下，威斯康星大学麦迪逊分校的John F. Berry教授将研究将三个金属原子串在一起如何改变这些模型分子线的电子结构。支持的工作包括合成分子尺度的线状化合物，这种化合物含有相似或不同金属原子之间的金属-金属键。物理性质的测量和计算分析将允许评估这些分子通过这些金属-金属键传输电荷的能力。这些和相关的研究对于推进量子计算领域的目标是重要的，因为它们为我们学习如何通过合成分子尺度设备控制自旋和电荷流提供了新的机会。将与美国和意大利的研究人员开展合作项目。该小组将设计并在科学传播计划、突出艺术与科学之间联系的演讲、旨在扩大代表性不足群体对科学的参与的推广工作以及其他与服务或教育相关的项目中发挥领导作用。因此，拟议的工作有可能广泛影响无机化学学科和整个化学领域，并在物理、电气工程和计算机科学领域产生影响。本研究项目的具体目标是开发能够精细控制支持杂三金属延伸金属原子链的轴向和赤道配体，以及金属原子身份和金属-金属相互作用类型的合成方法。控制轴向连接基团将允许这些分子有效地集成到分子电路中，从而可以进行电荷传输测量。将这些异金属分子中包含的金属原子类型从第一和第二行过渡元素（例如镍和钼）扩展到镧系元素和主族元素是一个主要目标。对赤道配体和金属同一性的修改应该允许填充的轨道能级（金属中的“费米”能级的分子模拟）被调整。Berry研究小组预计，将有可能获得具有羧酸衍生轴向配体的新分子，这将有助于我们在分子电导率测量中测试连接基团效应。新型金属-金属相互作用的发现有可能揭示分子二极管样行为，多维光谱测量旨在深入了解链内低能金属-金属振动与电子转移之间的耦合。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 the support of the Chemical Synthesis program in the Division of Chemistry, Professor John F. Berry of the University of Wisconsin – Madison will study how stringing three metal atoms together alters the electronic structures of these model molecular wires. The supported work includes synthesis of molecule-scale wire-like compounds that contain metal-metal bonds between similar or different metal atoms. Measurement of physical properties and computational analyses will allow for an assessment of the ability of these molecules to transport charge through these metal-metal bonds. These and related studies are important for advancing toward goals in the field of quantum computing, as they provide new opportunities for us to learn how to control spins and charge flow through synthetic molecule-scale devices. Collaborative projects with researchers in the US as well as in Italy will be pursued. The team will design and play leadership roles in science communication initiatives, presentations that highlight connections between arts and science, outreach efforts aimed at broadening participation in science by underrepresented groups, and other service- or education-related projects. The proposed work thus has the potential to broadly impact the discipline of inorganic chemistry and the field of chemistry as a whole, and has implications in areas of physics, electrical engineering, and computer science.The specific goals of this research project are to develop synthetic methods that allow for the fine control of the axial and equatorial ligands that support heterotrimetallic extended metal atom chains, as well as the metal atom identities and types of metal-metal interactions. Control over the axial linking groups will allow for these molecules to be effectively integrated into molecular circuitry so that charge transport measurements can be made. Expansion of the types of metal atoms included in these heterometallic molecules from first- and second-row transition elements (e.g., nickel and molybdenum) to lanthanide and main group elements is a major goal. Modification of the equatorial ligands as well as metal identities should allow for the filled orbital energy levels (the molecular analog of the “Fermi” level in metals) to be tuned. The Berry research team anticipates that it will be possible to access new molecules having carboxylate-derived axial ligands that will help us to test linking group effects in molecular conductivity measurements. Discovery of new types of metal-metal interactions has the potential to uncover molecular diode-like behavior, and multidimensional spectroscopy measurements are designed to provide insight into the coupling between low-energy metal-metal vibrations within the chain and electron transfer.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.