Control of Function and Reactivity in Lanthanide Chemistry by Tailored Ligand Design

本文所述的研究目标是控制化合物中金属离子的物理和化学性质。镧系金属的化合物是这项工作的重点，因为它们比其他金属具有重要的优势，包括更高的反应性，不同的选择性和理想的电子和核性质。镧系化学发展缓慢，因为这些金属需要特殊的配位环境才能形成活性化合物。例如，在催化作用中，必须在形成稳定的、可分离的化合物和具有足够反应活性的金属中心之间取得良好的平衡，以进行有用的化学转化。这里描述的新配位系统旨在实现两个截然不同的目的：(i)允许催化形成有机分子中的C-C、C-N和其他键；（ii）形成水和空气稳定的镧系化合物，这些化合物在医学成像（磁共振、伽马成像、荧光成像）或治疗（作为靶向抗癌药物的放射性镧系化合物）中具有制药应用。在镧系催化剂的促进下，获得新的有机分子对于开发具有不同寻常的电子、光学和磁性质的新药物和新材料至关重要。镧系化合物在医学中扮演着重要的角色，作为成像或靶向肿瘤破坏的药物剂。为构成本提案基础的镧系元素开发新的配位环境对于实现这些独特金属的实际潜力至关重要。

The goal of the research described in this proposal is to control the physical and chemical properties of metal ions in compounds. Compounds of the lanthanide metals are the specific focus of this work because they offer important advantages over other metals including higher reactivity, different selectivity and desirable electronic and nuclear properties. Lanthanide chemistry has developed slowly because these metals require special coordination environments to form reactive compounds. In catalysis, for example, a fine balance must be achieved between formation of stable, isolable compounds and metal centres with sufficient reactivity to carry out useful chemical transformations. The new coordination systems described here are designed to achieve two very different purposes: (i) to allow the catalytic formation of C-C, C-N and other bonds in organic molecules and (ii) to form water and air stable lanthanide compounds that have pharmaceutical applications in medical imaging (magnetic resonance, gamma imaging, fluorescence imaging) or therapy (radio-lanthanide complexes as targeted anti-cancer drugs). Access to new organic molecules, facilitated by lanthanide catalysts, is critical to developing new pharmaceuticals and materials with unusual electronic, optical and magnetic properties. Lanthanide compounds have assumed a major role in medicine, acting as the pharmaceutical agent for imaging or targeted tumor destruction. The development of new coordination environments for the lanthanides that forms the basis of this proposal is critical to realizing the practical potential of these unique metals.