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.

这项提案建立在Hutchison教授最近发现的一类新的螯合双环二酰胺配体，这些配体在结合亲和力对F-block元素的结合亲和力表现出显着增强，与基于马诺酰胺子结构的大型配体相比。使用分子力学建模的有理方法鉴定了新的配体类，即3,9-DIAZA-3,9- dialkylBicyclo [4.4.0] decane-2，10-二离子。预组织的双环结构理想地定位了两个羰基，以实现最佳金属配体相互作用。已经开发了这种配体类的高效且通用的合成，与几个类似的无循环透明体相比，离子提取实验表明，F-块离子的AFFMITY增强了3至500万倍。最初的发现表明，可以准备一类丰富的配体，其中可以广泛调整对F-块元素的结合亲和力。该提案的总体目标是确定可以通过综合理论，综合和测试程序合理设计和快速优化新的配体的方法。本提案中的三个主要目标旨在帮助阐明决定这一新的配体特性的设计标准。这些目标是（i）开发合成方法，可以允许配体结构进行广泛变化（范围从烷基和芳基取代基的性质和位置范围范围内到双环结构内的环尺寸），（ii）研究溶液和固态配位化学的溶液和固体配位化学，并将这些化学的材料造成了这些化学的作用，以使这些材料的作用融合到了这些ligant和（IIIIIIIIIIIIIIIIIIII层）（III IIIII（IIIIIIII）（III II II II II II））电影）。 通过该奖项，有机和大分子化学计划支持俄勒冈大学的詹姆斯·哈奇森教授的研究，其工作涉及配体设计，合成化学，旁观化学方法，配位化学，晶体学，溶剂提取和材料化学化学。这项工作将通过接触广泛的研究来增强学生的培训。它还将通过针对诸如核燃料后处理和高级废物管理等应用以及对荧光探针和传感器中灯笼的发光剂的敏感性来为社会做出贡献。