Molecules and Clusters with Actinide-Chalcogen Bonds

在这个由化学部门化学合成项目资助的项目中，罗格斯大学的约翰·布伦南教授探索了锕系元素与硫、硒和碲结合的基本化学，包括分子和纳米级材料的合成和表征。了解锕系元素如何与这些硫元相互作用可以提高我们在核燃料后处理和环境废物修复中分离锕系离子的能力。该项目从合成和表征具有多种硫代酚酸配体的选择分子锕系化合物开始。为了评估金属、氧化态、硫代酚酸酯和路易斯碱供体如何影响结构和成键，研究了一系列具有潜在共价键特征的分子。这些将作为理论计算的模型系统，以揭示键合的性质，并预测锕系元素系统的化学反应性。该分子产物可作为低温合成纳米级锕系元素簇和固态材料的起始原料。离子（氧化物、氟化物）和共价（硫化物、硒化物、碲化物）配体都被纳入簇核，硫代酚酸盐配体覆盖簇表面，抑制固态产物的形成。锕系元素分子、纳米级簇和固态材料的电子和磁性之间的关系是通过对这些分子硫代酚酸酯和纳米级产物的测量来定义的。这项工作的多学科性质为本科生和研究生提供了一系列潜在的职业道路。

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.