International Collaboration in Chemistry: A Combined Experimetal and Theoretical Study of Redox-Active Fe4O4-Cubanes

这个奖项在无机，生物无机和有机化学计划支持研究教授拉斐尔G。Raptis在波多黎各大学研究八核铁簇，其中包含一个Fe 4 O 4立方烷核心周围的四个外围FeIII中心，并将研究扩展到1-，2-，3-和4-电子还原类似物。目标是表征在电化学实验中观察到的跨越Fe（III）8和Fe（III）4Fe（II）4极限的每个混合价态。在波多黎各大学的重点将是新的集群的合成能够支持更高度降低氧化水平和他们的表征使用广泛的物理化学技术。伏安法、衍射、原位紫外-可见-近红外光谱电化学和XPS将在内部进行，而磁化学性质、EPR和穆斯堡尔谱将在各自领域的领导者的实验室进行测量。格拉斯哥大学的研究小组将利用对称性破缺密度泛函理论探索这些化合物的电子结构。我们的目的是通过建立一个直接的对应关系观察和潜在的电子结构Fe 8集群在这个建议中描述的物理化学测量的信息内容最大化提供了一个独特的机会，研究混合价在一个离散的分子物种在一个前所未有的范围内的氧化态。 该项目将把波多黎各大学和格拉斯哥大学的既定研究方案联系起来，这两所大学都侧重于顺磁性金属簇的结构。青年研究人员通过在国际实验室长期停留交流互补思想和专业知识的机会是研究计划的一个关键因素，将有助于在两个群体之间建立长期的联系。该国际合作化学研究项目由NSF和英国工程与物理科学研究理事会（EPSRC）共同支持。这项研究也得到了NSF国际科学与工程办公室（OISE）的支持。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Raphael G. Raptis at the University of Puerto Rico to investigate an octanuclear iron cluster, which contains an Fe4O4 cubane core surrounded by four peripheral FeIII centers and would extend studies to the 1-, 2-, 3- and 4-electron reduced analogues. The goal is to characterize each of the mixed-valent states spanning the Fe(III)8 and Fe(III) 4Fe(II)4 limits observed in the electrochemical experiment. The focus at the University of Puerto Rico will be on the synthesis of new clusters capable of supporting the more highly reduced oxidation levels and their characterization using a wide range of physicochemical techniques. Voltammetry, diffraction, in situ UV-Vis-NIR spectroelectrochemistry and XPS will be conducted in-house, while magnetochemical properties, EPR and Mossbauer spectra will be measured in the laboratories of established collaborators who are leaders in their fields. The research team at the University of Glasgow will explore the electronic structure of these compounds using broken-symmetry density functional theory. The aim is to maximize the information content of the physicochemical measurements by establishing a direct correspondence between observation and the underlying electronic structureThe Fe8 clusters described in this proposal offer a unique opportunity to study mixed valence in a discrete molecular species across an unprecedented range of oxidation states. This project will link established research programms at the University of Puerto Rico and the University of Glasgow, both of which focus on the structure of paramagnetic metal clusters. The opportunity for young researchers to exchange complementary ideas and expertise through extended stays in international laboratories is a key element of the research programs, and will help to establish long-lasting links between the two groups. This International Collaborative Chemistry research project is supported jointly by NSF and the Engineering and Physical Sciences Research Council (EPSRC) in the United Kingdom. The study is also supported by the Office of International Science and Engineering (OISE) at NSF.