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

用于增强 f 区元素结合的构象预组织二酰胺配体：新配体、配位配合物和功能材料

• 批准号: 0213563
• 负责人: James Hutchison
• 金额: $ 35.1万
• 依托单位: University of Oregon Eugene
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-08-15 至 2007-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0213563&HistoricalAwards=false
• 关键词: Conformationally; Preorganized; Diamide; Ligands; Enhanced

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.

这一建议建立在Hutchison教授最近发现的一类新的螯合双环二酰胺配体的基础上，与基于丙二酰胺子结构的大类配体相比，该配体对f-区元素的结合亲和力表现出显着增强。新的配体类别，3，9-二氮杂-3，9-二烷基双环[ 4.4.0]癸烷-2，10-二酮，使用合理的方法，利用分子力学建模进行了鉴定。预组装的双环结构理想地定位两个羰基以实现最佳的金属-配体相互作用。已经开发了这种配体类的高效和通用的合成，并且离子萃取实验已经显示，与几种类似的无环二酰胺相比，f-区离子的亲和力增强了300万至500万倍。这一最初的发现表明可以制备丰富的配体类别，其中可以广泛地调节对f区元件的结合亲和力。该提案的总体目标是确定新配体可以通过集成的理论，合成和测试程序合理设计和快速优化的方法。在这个建议中的三个主要目标的目的是帮助阐明的设计标准，规定这类新的配体的性能。这些目标是（i）开发允许配体结构广泛变化的合成方法（从烷基和芳基取代基的性质和位置到双环结构内的环尺寸），（ii）研究新配体的溶液和固态配位化学，并将该化学与配体设计联系起来，以及（iii）将这些配体并入功能材料中（聚合物、有机薄膜）。 有了这个奖项，有机和高分子化学计划支持俄勒冈州大学的詹姆斯·哈奇森教授的研究，他的工作涉及配体设计，合成化学，光谱方法，配位化学，晶体学，溶剂萃取和材料化学。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放射性废物管理等应用以及荧光探针和传感器中镧系元素发光的敏化剂来为社会做出贡献。