New Actinide Ligand Multiple Bonds Supported by Triamidoamine Ligands

在过去的十年中，我们已经发现，三酰胺基胺配体是理想的辅基，与它支持新的锕系元素-配体连接，特别是多个键，固有地表现出共价性，使它们成为探针的典范。然而，仍有许多目标有待实现，这个博士生的目标是一个综合的子集。通过合成创新，我们将：（i）使用电子缓冲剂来抵消可能使这种键不稳定的不稳定电荷积累，以新的锕系元素双键键为目标;（ii）使用经修饰的辅助配体来靶向新的锕系元素三键键;（iii）使用英国国家EPSRC EPR设施，使用脉冲EPR来探测现有和新的锕系元素配体多重键的共价性;（iv）在国家设施中使用配体K边和金属M边XANES和RIXS技术检查现有和新的锕系元素-配体多重键，以从互补的角度进一步探测这些键的共价性。因此，该项目涉及有机和无机合成化学，以及使用先进的结构，光谱，磁性和计算表征技术。此外，学生将接受放射性化学品和高灵敏度化合物的安全处理，开发新的合成方法，管理复杂的表征方法组合和可转移技能的培训。这个项目将解决有关锕系元素的基本性质的基本问题，并提供一个早期的职业研究人员在放射化学训练。该项目与EPSRC化学结构、配位化学、化学合成方法学和磁性/磁性现象领域直接相关。

Over the past decade we have found that triamidoamine ligands are the ideal ancillaries with which to support novel actinide-ligand linkages, and in particular multiple bonds that inherently exhibit covalency, making them exemplars to probe. However, there are many targets still to be realised and this PhD studentship targets an integrated sub-set. Through synthetic innovation we will: (i) target new actinide-element double bond linkages using electronic buffers to offset destabilising charge build-up that can make such linkages unstable; (ii) target new actinide-element triple bond linkages using modified ancillary ligands; (iii) probe the covalency of existing and new actinide-ligand multiple bonds using pulsed EPR using the UK National EPSRC EPR Facility; (iv) examine existing and new actinide-ligand multiple bonds using ligand K-edge and metal M-edge XANES and RIXS techniques at national facilities to further probe the covalency of these linkages from a complementary perspective. This project thus involves organic and inorganic synthetic chemistry, and the use of advanced structural, spectroscopic, magnetic, and computational characterisation techniques. Further, the student will be trained in the safe handling of radiochemicals and highly sensitive compounds, developing novel synthetic approaches, managing a complex portfolio of characterisation methods, and transferrable skills. This project will address basic questions about the fundamental properties of actinide elements and provide a early career researcher trained in radiochemistry. This project is directly relevant to the EPSRC chemical structure, co-ordination chemistry, chemical synthetic methodology, and magnetism/magnetic phenomena areas.