Probing Actinide Covalency using NMR Spectroscopy and DFT Calculations

领域：合成配位化学，计算与理论化学，分析科学锕系元素科学的中心目标是更好地量化锕系元素-配体键的共价，并将其与元素周期表中的其他元素联系起来。实验探测锕系键的共价是具有挑战性的；共价的实验测量方法很少。然而，对于那些在接近热力学汇的简单系统中仍然隐藏的特征的新分子，我们可以使用核磁共振波谱在实验上探测锕系元素的共价。之前（Nat. common . 2021, 12，文章号5649），我们证明了可以使用15N NMR波谱（溶液和固态MAS）探测铀氮三键的共价，揭示了前所未有的核磁共振波谱特性和锕系元素的共价。实验方法和计算方法的结合对这一成功至关重要。在这个项目中，你将准备一系列现有的和新的锕系元素配合物，有时带有同位素标签，除了用通常的分析技术来表征它们之外，你还将用详细的核磁共振和计算研究来探测锕系元素-配体键的共价，以量化共价。我们的总体目标是，通过研究各种相关的配合物和核磁共振核，建立我们对锕系元素共价的理解。

AREAS: SYNTHETIC COORDINATION CHEMISTRY, COMPUTATIONAL AND THEORETICAL CHEMISTRY, ANALYTICAL SCIENCE A central aim of actinide science is to better quantify the covalency of actinide-ligand bonding, and to relate this to elements across the rest of the periodic table. Experimentally probing the covalency of actinide bonding is challenging; there are few experimental measures of covalency. Nevertheless, with novel molecules, that display traits which remain hidden in simple systems close to thermodynamic sinks, we can use NMR spectroscopy to probe actinide-covalency experimentally.Previously (Nat. Commun. 2021, 12, article number 5649), we showed that the covalency of a uranium-nitride triple bond could be probed using 15N NMR spectroscopy (solution and solid-state MAS), revealing unprecedented NMR spectroscopic properties and actinide covalency. The marriage of experimental and computational methods was essential to this success.In this project, you will prepare a range of existing and novel new actinide complexes, sometimes with isotopic labels, and, in addition to characterising them with the usual range of analytical techniques, will probe the covalency of the key actinide-ligand linkages with detailed NMR and computational studies to quantify the covalency. Our overall aim is, through the study of various related complexes and NMR nuclei, to build our understanding of actinide covalency.