Molecules and Clusters with Actinide-Chalcogen Bonds

在这个由化学系化学合成计划资助的项目中，罗格斯大学的约翰·布伦南教授探索了鳗系元素与硫族元素硫、硒和碲结合的基础化学，包括分子和纳米材料的合成和表征。在核燃料后处理和环境废物修复中，对榄系元素如何与这些硫族元素相互作用的了解提高了我们分离鳗系元素离子的能力。该项目首先合成和表征了具有各种硫属配体的精选分子鳗系化合物。以一系列具有潜在共价键特征的分子为目标，研究金属、氧化态、硫杂金属和Lewis碱施主对结构和成键的影响。这些将作为理论计算的模型系统，以揭示键的性质并预测鳗系元素的化学反应活性。这些分子产物被用作低温合成纳米级鳗系元素簇合物和固态材料的起始原料。离子(氧化物、氟化物)和共价(硫化物、硒、碲化物)配体都被结合到簇核中，其中硫属配体覆盖簇表面并抑制固态产物的形成。通过对硫化物和纳米级分子产物的测量，确定了这些分子、纳米级团簇和固态材料的电子和磁性之间的关系。这项工作的多学科性质为本科生和研究生提供了一条通往一系列潜在职业道路的入口。

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor John Brennan of Rutgers University probes the fundamental chemistry of the actinide elements combined with the chalcogens sulfur, selenium, and tellurium, including the synthesis and characterization of both molecular and nanoscale materials. An understanding of how actinides interact with these chalcogens improves our ability to separate actinide ions in nuclear fuel reprocessing and environmental waste remediation.The project begins with the synthesis and characterization of select molecular actinide compounds with a variety of chalcogenolate ligands. A series of molecules with potential covalent bonding character are targeted in order to evaluate how the metal, oxidation state, chalcogenolate, and Lewis base donors influence structure and bonding. These will serve as model systems for theoretical calculations to uncover the nature of the bonding and to predict the chemical reactivity in actinide systems. The molecular products are used as starting materials in the low-temperature synthesis of nanoscale actinide clusters and solid-state materials. Both ionic (oxide, fluoride) and covalent (sulfide, selenide, telluride) ligands are incorporated into cluster cores, with chalcogenolate ligands that cap the cluster surface and inhibit the formation of solid-state products. The relationships between the electronic and magnetic properties of actinide molecules, nanoscale clusters, and solid-state materials are defined by measurements on these molecular chalcogenolate and nanoscale products. The multidisciplinary nature of this work affords undergraduate and graduate students an entrée to a range of potential career paths.