Chemistry of Deltahedral Zintl Ions and their Organically-Functionalized Derivatives

该奖项在无机，生物无机和有机物化学计划支持由教授Slavi Sevov在圣母大学的主群三角形簇（Zintl离子）的反应性研究，无论是同原子和杂原子（包括一些最近发现的铋/过渡金属物种）。 使用各种有机卤化物和炔，各种有机基团将被添加到九原子锗簇[Ge 9]n-（n = 4，3，2）。这些反应的产物分别是单-和二-取代的簇[R-Ge 9]3-和[R-Ge 9-R]2-，其中R基团可以是简单的烷基或可以具有双键、苯基或吡啶环以及其它官能团。这些研究将扩展到该组中的其他元素，它们形成相同的九原子簇，即[Si 9]n-，[Sn 9]n-和[Pb 9]n-，以及杂原子簇，如（[Ge 9]-x[Sn x]）n-，（In 4 Bi 5）3-和（Tl 4 Bi 5）3-。所提出的反应集中在有机取代基上，并通过将积累的知识应用于新的底物，利用在其他化学领域如有机和有机金属化学中充分研究的反应。例如，烯基-Zintl离子如[CH 2 = CH-Ge 9-CH= CH 2]2-中的双键可能易于硼氢化和/或聚合。吡啶取代的Zintl离子可能能够通过吡啶氮与过渡金属配位并形成分子或扩展结构。本课程将探讨小分子团簇的几何形状与成键方式，以及它们的性质与反应性之间的关系。所提出的集群的兴趣作为潜在的前体新的经典材料（金属间化合物，扩展结构）以及纳米材料（纳米棒，薄膜，表面接枝）具有新颖的电子和磁性。该项目将作为一种工具，通过与少数群体研究生教育组织的关系，吸引来自代表性不足群体的学生和博士后研究员。此外，还与占少数的克拉克大学（亚特兰大）、泽维尔大学（新奥尔良）、圣玛丽学院和圣爱德华学院（圣安东尼奥）发展关系，以便从这些大学招收暑期本科生和研究生。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Slavi Sevov at Notre Dame University on the reactivity of main-group deltahedral clusters (Zintl ions), both homo- and hetero-atomic (including a number of recently discovered bismuth/transition metal species). Using a variety of organic halides and alkynes, a variety of organic groups will be added to nine-atom germanium clusters [Ge9]n- (n = 4, 3, 2). The products of these reactions are mono- and di-substituted clusters [R-Ge9]3- and [R-Ge9-R]2-, respectively, where the R groups can be simple alkyl groups or can have double bonds, phenyl or pyridine rings, and other functionalities. These studies will be extended into the other elements of this group, which form the same nine-atom clusters, i.e. [Si9]n-, [Sn9]n-, and [Pb9]n-, as well as into heteroatomic clusters such as ([Ge9]-x[Snx])n-, (In4Bi5)3-, and (Tl4Bi5)3-. The proposed reactions focus on the organic substituents and take advantage of well-studied reactions in other areas of chemistry such as organic and organometallic chemistry by applying the accumulated knowledge to the new substrates. For example, the double bonds in alkenyl-Zintl ions such as [CH2=CH-Ge9-CH=CH2]2- may be susceptible to hydroboration and/or polymerization. Pyridine-substituted Zintl ions may be able to coordinate to transition metals via the pyridine nitrogen and to form molecular or extended structures. The relation between the geometry and bonding of small molecular clusters, and their properties and reactivity will be investigated. The proposed clusters are of interest as potential precursors to new classical materials (intermetallics, extended structures) as well as nano materials (nanorods, thin films, surface grafting) with novel electronic and magnetic properties. The project will be used as a tool to attract both students and postdoctoral fellows from underrepresented groups through a relationship with the Graduate Education for Minorities organization. Relationships are also being developed with the predominantly minority Clark University (Atlanta), Xavier (New Orleans), and St. Mary and St. Edward colleges (San Antonio) in order to bring summer undergraduate students and to recruit graduate students from these universities.