Lanthanide and actinide m-terphenyl complexes

该项目旨在发展低OS f-区（M2+）离子的化学性质，以更深入地了解影响其价电子构型（VEC）的性质，以及不同VEC驱动的不同化学的潜力。当代的低氧化态（OS）、M2+、f-区化学已经定义了两类M2+离子（其中M =镧系（Ln）或锕系（An）金属）：fn+1或fnd 1-在某些情况下对于具有不同配体组的相同金属都存在。在这里，我们将针对分子设计功能，故意调制稀土，Ln，和早期的锕系元素的离子在低OS的电子配置。这将提供对这些离子的物理化学性质的前所未有的控制。我们将通过以下方式实现这一目标：1）使用模块化框架合成低OS f-嵌段络合物，其中配体供体原子可以改变而不改变整体立体化学性质; 2）使用适合高级光谱表征的供体元素; 3）通过磁性（SQUID）、磁共振（NMR、EPR）、X射线吸收光谱（在金属边缘）表征分子，以加深对其电子结构的理解。这种系统的方法还没有应用到这个新兴的研究领域，是一个合乎逻辑的下一步，以扩大其前沿。这项工作将产生基础知识，通知未来的工作到配置控制的f-区离子，和氧化还原驱动的镧系元素/锕系元素chemical.Questions：-我们可以使用软和硬施主配体支持金属芳烃相互作用，以隔离低氧化态镧系元素和锕系元素配合物？-这些配合物的电子结构是什么，电子密度是否存在于金属或配体上？这会随着捐赠者的类型而改变吗？这些低氧化态配合物的反应像传统的镧系元素配合物，或更像过渡金属？方法：-设计和合成配体。-使络合物处于容易获得的氧化态。将络合物还原至较低的形式氧化态。使用最先进的实验和理论方法进行表征。使用经典的过渡金属反应类研究反应性。Remit / themes：-合成配位化学/-计算和理论化学。-凝聚态物质：电子结构。凝聚态物质：磁性与磁性材料。

This PhD studentship supports an EPSRC New Investigator Award application, and thus the description matches that project.This project seeks to develop the chemistry of low OS f-block (M2+) ions towards a deeper understanding of the properties that affect their valence electron configuration (VEC), and the potential for divergent chemistry driven by different VECs. Contemporary low oxidation state (OS), M2+, f-block chemistry has defined two classes of M2+ ion (where M = a lanthanide (Ln) or actinide (An) metal): fn+1 or fnd1 - in some cases both exist for the same metal with different ligand sets. Here we will target molecular design features to deliberately modulate the electronic configuration of rare-earth, Ln, and early actinide An ions in low OSs. This will afford unprecedented control over the physicochemical properties of these ions. We will achieve this by: 1) synthesising low OS f-block complexes using modular frameworks where ligand donor atoms can be altered without changing overall stereochemical properties; 2) using donor elements which are amenable to advanced spectroscopic characterisation; 3) characterising molecules by magnetism (SQUID), magnetic resonance (NMR, EPR), X-ray absorption spectroscopy (at metal edges), to deepen understanding of their electronic structure. This systematic approach has not yet been applied to this nascent research area and is a logical next step to expand its frontier. This work will produce fundamental knowledge to inform future work into configuration control of f-block ions, and redox-driven lanthanide/actinide chemistry.Questions:- Can we use soft- and hard-donor ligands which support metal-arene interactions to isolate low-oxidation state lanthanide and actinide complexes?- What is the electronic structure of these complexes, does the electron density reside on the metal or ligand?- Does this change with the donor type?- Do these low oxidation state complexes react like traditional lanthanide complexes, or more like transition metals?Approach:- Design and synthesize ligands.- Make complexes in readily available oxidation states.- Reduce complexes to lower formal oxidation states.- Characterize using state of the art experimental and theoretical approaches.- Study reactivity using classical transition metal reaction classes.Remit / themes:- Synthetic coordination chemistry/- Computational and theoretical chemistry.- Condensed matter: electronic structure.- Condensed matter: magnetism and magnetic materials.