sigma-Aromatic Actinide-Actinide Bonding: A New Frontier in f-Block Chemistry

元素周期表主要由金属组成。因此，金属-金属键合是一个巨大的新兴领域，它是推动我们对结构，键合，反应性和磁性的理解逐步变化的基础。在177年的时间里，s-、p-和d-嵌段已经产生了许多不同的金属-金属键合图案的常规可分离的例子。相比之下，可分离的锕系元素-锕系元素（An-An）键合，合成An化学的首要目标之一，一直难以捉摸，排除了反应性模式的评估，这是理解金属-金属键合的核心原则。这个冒险的项目旨在利用我们最近发现的分子可分离的钍-钍键合（Nature 2021，598，72-75），其描述了令人惊讶的σ-芳族键合以记录周期表的第6和第7行的主量子数和多电子小分子活化反应性。基于我们的初步结果，该项目旨在扩大An-An配合物的范围，确定其反应趋势，并使用全面的实验和理论表征技术来探测其电子结构和物理化学性质。这将涉及范围广泛的项目伙伴以及国家和国际研究设施，它们将共同采取一种连贯和相互交织的办法。这项研究对于核部门具有战略重要性，因为它将保留一名熟练的ECR并在已知的英国技能短缺领域培训两名新的ECR，并与利益相关者一起开发处理放射性元素的“最佳实践”方法，从而促进学术界的知识转移：工业界接口。通过研究该项目中概述的化合物，将开发分析技术的新应用，由此产生的方法学进步将在内部发展这些学科的能力和健康，而且更广泛地说，因为这些技术涉及在许多其他领域工作的设施和研究人员，这些领域可以受益于新工作方式的转移。这个项目是及时开发和我们的初步结果表明，工作是可实现的和有影响力的。因此，我们要求与拟议工作的范围和雄心相称的资金，以发展这一有前途的领域，以便利用我们的突破，保持在这个新创建的令人兴奋的领域的国际前沿，并产生对An-chemistry具有国际意义的结果。

The Periodic Table is mainly composed of metals. Thus, metal-metal bonding is a vast burgeoning field that is fundamental to driving step-changes in our understanding of structure, bonding, reactivity, and magnetism. Over 177 years the s-, p-, and d-blocks have produced numerous routinely isolable examples of varied metal-metal bonding motifs. In contrast, isolable actinide-actinide (An-An) bonding, one of the top goals of synthetic An-chemistry, has remained elusive in all that time, precluding assessment of reactivity patterns that are a central tenet of understanding metal-metal bonding. This adventurous project aims to exploit our recent discovery of molecular isolable thorium-thorium bonding (Nature 2021, 598, 72-75), which describes surprising sigma-aromatic bonding to record principal quantum number 6 and 7th row of the Periodic Table and multi-electron small molecule activation reactivity. Building on our preliminary result, this project seeks to expand the range of An-An complexes, determine their reactivity trends, and probe their electronic structure and physicochemical properties using a comprehensive range of experimental and theoretical characterisation techniques. This will involve a wide range of project partners and national and international research facilities brought together into a cohesive and interleaved approach. This research is strategically important with respect to the nuclear sector, as it will retain a skilled ECR and train two new ones in a known UK skills-shortage area, and together with stakeholders we will develop 'best practice' methods for handling radioactive elements, thus promoting knowledge transfer at the academia:industry interface. By studying the compounds outlined in the project, new applications of analytical techniques will be developed, and the resulting methodological advances will develop the capability and health of those disciplines in-house, and also more broadly because those techniques involve facilities and researchers that work across many other areas that could benefit from the transfer of new working ways. This project is timely to develop and our preliminary results show the work is achievable and impactful. Thus, we request funds commensurate with the scope and ambition of the proposed work to develop this promising area in order to capitalise on our breakthrough, stay at the international forefront of this newly created and exciting field, and generate results of international significance to An-chemistry.