Defining the Electronic Structures of f-Block Heavy Pnictogen Compounds

F-块元素，镧系元素(Ln)和辐系元素(An)，由于其独特的物理化学性质和在核燃料循环中的应用，具有巨大的技术重要性。我们认为，Ln和一个重族15化合物的合成和研究将对f-块电子结构提供新的见解，并将为未来的探索开辟多条途径。我们将合成含有Pn-Si键的单核Ln/An Pn化合物，这些Pn-Si键很容易裂解形成多核簇合物，并直接在Ln/An位安装锌离子形成多核簇合物。这些化合物将通过广泛的表征技术进行研究，并将进行精心挑选的反应性研究。这项建议汇集了一个具有独特技能组合的团队，以提供：(I)结构相似的新型Ln和重pnitogen(Pn)分子化合物和多尼古丁基团簇；(Ii)Ln/An-Pn和Ln/An=Pn键的反应性研究；以及(Iii)全面的物理研究和高水平计算以绘制电子结构图。明确定义的分子化合物和簇将提供可转移的数据，这些数据以后可以应用于工业上相关的大宗磷化物和砷化物材料。学生将使用Schlenk线和手套箱技术合成一系列对空气和湿度敏感的Ln/An PN化合物。这些化合物将与我们的合作者一起通过实验技术进行研究，包括溶液和固体核磁共振、EPR、UV/VIS/NIR、发光、IR和X射线吸收/发射光谱、循环伏安、元素分析、SQUID磁测量、单晶和粉末X射线衍射；物理数据将通过高密度泛函理论和从头计算进行基准。结果将在适当的情况下在黄金标准期刊、国际会议和新闻稿中传播。当发现应用时，知识产权将受到专利保护，并在需要时进行商业化。符合EPSRC的要求本建议与EPSRC最新的战略计划和交付计划、愿景和目标完全一致。我们将加强EPSRC“合成配位化学”的研究领域，为我们创造性的合成方法提供可应用于其他项目的目标分子。通过先进的物理和计算研究对这些化合物进行表征，将推动技术开发方面的创新和进步，为EPSRC的多个研究领域做出重大贡献，包括“分析科学”、“化学结构”和“计算和理论化学”；支持这一建议的合作伙伴包括英国的计算化学家、EPSRC国家EPR设施和DLS。这名博士生将接受对空气敏感的液氮和化学方面的培训，这对英国学术界、核工业和经济具有战略意义。

ObjectivesThe f-block elements, the lanthanides (Ln) and actinides (An), are of huge technological importance due to both their unique physicochemical properties and their use in nuclear fuel cycles. We propose that the synthesis and study of Ln and An heavy group 15 compounds will provide new insights into f-block electronic structure and will open up multiple pathways for future exploration. We will synthesise mononuclear Ln/An Pn compounds containing Pn-Si bonds, which can be readily cleaved to form polynuclear clusters, and to directly install Zintl ions at Ln/An sites to form polynuclear clusters directly. These compounds will be studied by a wide range of characterisation techniques, and judiciously selected reactivity studies will be performed.This proposal brings together a team with a unique combination of skills to deliver: (i) Structurally analogous families of novel Ln and An heavy pnictogen (Pn) molecular compounds and polypnictogen clusters; (ii) Reactivity studies of Ln/An-Pn and Ln/An=Pn bonds; and, (iii) Comprehensive physical studies and high-level calculations to map electronic structures. Well-defined molecular compounds and clusters will provide transferrable data that can be later applied to industrially relevant bulk phosphide and arsenide materials. ApproachThe student will synthesise a range of air- and moisture-sensitive Ln/An Pn compounds, using Schlenk line and glove box techniques. Together with our collaborators these compounds will be studied by experimental techniques including solution and solid-state NMR, EPR, UV/Vis/NIR, luminescence, IR and X-ray absorption/emission spectroscopies, cyclic voltammetry, elemental analysis, SQUID magnetometry, single crystal and powder X-ray diffraction; physical data will be benchmarked by high-level density functional theory and ab initio calculations. Results will be disseminated in gold standard journals, international conferences, and press releases when appropriate. When applications are discovered, IP will be protected by patents and commercialised when required.Fit to EPSRC RemitThis proposal is fully aligned to the most recent EPSRC Strategic Plan and Delivery Plan, Vision and Objectives. We will strengthen the EPSRC research area of "Synthetic Coordination Chemistry" as our creative synthetic methods to provide the target molecules can be applied to other projects. Characterisation of these compounds by advanced physical and computational studies will drive innovations and progress in technique development to make major contributions to multiple EPSRC research areas, including "Analytical Science", "Chemical Structure" and "Computational and Theoretical Chemistry;" collaborations that underpin this proposal with UK-based computational chemists, the EPSRC National EPR Facility and DLS are already in place. The PhD student will be trained in air-sensitive Ln and An chemistry, of strategic benefit to UK academia, the nuclear industry and the economy.