REVERSIBLE REDOX CONTROL OF MACROCYCLE-CATION BINDING

大环-阳离子结合的可逆氧化还原控制

• 批准号: 3284151
• 负责人: LUIS A ECHEGOYEN
• 金额: $ 12.92万
• 依托单位: UNIVERSITY OF MIAMI CORAL GABLES
• 依托单位国家: 美国
• 财政年份: 1984
• 资助国家: 美国
• 起止时间: 1984-07-01 至 1988-02-29
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3284151
• 关键词: cations; chemical binding; electrochemistry; electron spin resonance spectroscopy; electron transport; nuclear magnetic resonance spectroscopy; oxidation reduction reaction

A new series of macrocyclic polyether derivaties will be synthesized and their metal cation binding properties will be measured before and after one-electron reductions. All compounds in this series contain functional groups attached to the polyether macroring which are susceptible to one and/or two electron reduction. Preliminary results show that the anionic functional groups participate strongly in the metal cation binding process together with the macroring donor atoms. In some of the studied cases the binding constants increase by a factor of 25,000 after electron transfer is effected. The proposed systems have been designed to optimize the stability of the anionic species as well as to afford extra flexibility by providing the possibility of one or two-electron reduction. This added flexibility sets the basis for a "tunable" molecular switch, which can be turned-on to complex specific cations (an element of selectivity). The binding characteristics will be determined using electrochemical techniques, ESR spectroscopy, and NMR spectroscopy. Transport kinetics through synthetic membrance will be used to study selectivity as well as transport efficiencies as a function of applied voltage and current. Attempt will be made to isolate the alkali metal-macrocyclic polyether complexes as solids.

将合成一系列新的大环聚醚衍生物，并 它们的金属阳离子结合性能将在前后进行测量 单电子还原。本系列中的所有化合物都含有官能团 附着在聚醚大环上的基团对一种 和/或两个电子还原。初步结果表明，阴离子 官能团强烈参与金属阳离子结合过程 连同宏观配位的施主原子。在一些研究的案例中， 电子转移后结合常数增加25,000倍 已生效。 建议的系统旨在优化系统的稳定性 以及提供额外的灵活性，通过提供 一个或两个电子还原的可能性。这增加了灵活性集 可调谐分子开关的基础，它可以开启到 复杂的特定阳离子(一种选择性元素)。 结合特性将使用电化学法确定 技术、ESR波谱和核磁共振波谱。输运动力学 通过合成膜将被用来研究选择性以及 作为施加电压和电流的函数的传输效率。 将尝试分离碱金属-大环聚醚 络合物作为固体。