Conformationally Preorganized Diamide Ligands for Enhanced Binding of f-Block Elements: New Ligands, Coordination Complexes and Functional Materials

这一建议建立在Hutchison教授最近发现的一类新的螯合双环二胺配体的基础上，与基于丙二酰胺亚结构的大类配体相比，这种配体与f-块元素的结合亲和力显著增强。新的配体类，3，9-二氮-3，9-二烷基双环[4.4.0]癸烷-2，10-二酮，用合理的方法利用分子力学模型进行了鉴定。预先组织的双环结构理想地定位了两个羰基，以实现最佳的金属-配体相互作用。已经开发出一种高效和通用的这类配体的合成方法，离子提取实验表明，与几种类似的无环二胺相比，f-嵌段离子的亲和力提高了300-500万倍。这一初步发现表明，可以制备一类丰富的配体，其中f-块元件的结合亲和力可以广泛调节。这项提议的总体目标是通过一个集成的理论、合成和测试计划来确定能够合理设计和快速优化新配体的方法。这项提案的三个主要目标旨在帮助阐明决定这类新配体性质的设计标准。这些目标是(I)开发允许配体结构(从烷基和芳基取代基的性质和位置到双环结构中的环大小)广泛变化的合成方法，(Ii)研究新配体的溶液和固体配位化学，并将这种化学与配体设计联系起来，以及(Iii)将这些配体结合到功能材料(聚合物、有机薄膜)中。通过该奖项，有机和高分子化学项目支持俄勒冈大学James Hutchison教授的研究，他的工作涉及配体设计、合成化学、光谱方法、配位化学、结晶学、溶剂提取和材料化学。这项工作将通过接触广泛的研究来加强学生的培训。它还将通过针对核燃料后处理和高水平废物管理以及荧光探测器和传感器中的稀土发光敏化剂等应用，为社会做出贡献。

This proposal builds off Professor Hutchison's recent discovery of a new class of chelating bicyclic diamide ligands that exhibit dramatic enhancements in binding affinity for the f-block elements compared to the large class of ligands based upon the malonamide substructure. The new ligand class, the 3,9-diaza-3,9- dialkylbicyclo[ 4.4.0]decane-2, 10-diones, were identified using a rational approach utilizing molecular mechanics modeling. The preorganized bicyclic structure ideally positions the two carbonyl groups for optimal metal-ligand interaction. A highly efficient and versatile synthesis of this ligand class has been developed and ion extraction experiments have shown a 3 to 5 million-fold enhancement in affmity for f- block ions when compared to several analogous acyclic diamides. This initial discovery suggests a rich class of ligands can be prepared wherein the binding affinity for f- block elements can be widely tuned. The overall goal of this proposal is to identify methods by which the new ligands can be rationally designed and rapidly optimized through an integrated theory, synthesis and testing program. The three primary objectives in this proposal are designed to help elucidate the design criteria that dictate the properties of this new class of ligands. These objectives are (i) developing synthetic methods that permit wide variation of the ligand structure (ranging from the nature and position of alkyl and aryl substituents to the ring sizes within the bicyclic structure), (ii) investigating the solution and solid-state coordination chemistry of the new ligands and relating this chemistry back to the ligand design and (iii) incorporating these ligands into functional materials (polymers, organic thin films). With this Award, the Organic and Macromolecular Chemistry Program supports the research of Professor James Hutchison of the University of Oregon whose work involves ligand design, synthetic chemistry, spectroscopy methods, coordination chemistry, crystallography, solvent extraction, and materials chemistry. This work will enhance student training through exposure to a wide range of research. It will also contribute to society by targeting such applications as nuclear fuel reprocessing and high-level waste management, and sensitizers for lanthanide luminesence in fluorescent probes and sensors.