Developing electron transfer from chiral circularly polarized luminescence-based photocatalysts towards selective radical cross-coupling reactions

开发从手性圆偏振发光光催化剂到选择性自由基交叉偶联反应的电子转移

• 批准号: 10663899
• 负责人: Gael Ung
• 金额: $ 24.15万
• 依托单位: UNIVERSITY OF CONNECTICUT STORRS
• 依托单位国家: 美国
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/10663899
• 关键词: Cerium; Chemistry; Complex; Coupled; Coupling; Development; Electron Transport; Electrons; Engineering; Exciton; Exhibits; Fluorescence; Funding; Generations; Goals; Harvest; Laboratories; Lanthanoid Series Elements; Lead; Left; Ligands; Light; Methodology; Methods; Pathway interactions; Photosensitizing Agents; Population; Property; Publishing; Reaction; Reagent; Research; Research Project Grants; Side; Source; Technology; Transition Elements; Vertebral column; absorption; base; design; emission spectroscopy; light emission; luminescence; manufacturing process; next generation; programs; virtual

Summary The long-term goal of the proposed project is to develop the next generation of cross-coupling reactions. We aim at eliminating the need of differentiation between coupling partners, while retaining high reactivity and selectivity by utilizing polarized radical species. We will take advantage from the fact that a polarized radical species will only react with another radical species with the opposite polarization. The central hypothesis is that complexes emitting strong circularly polarized luminescence (CPL) possess a high population of high energy polarized excitons that can be harvested for reactivity. CPL is the emission of light with preferential circular polarization and has emerged as the next generation light source. Lanthanide complexes are the best CPL emitters, and cerium complexes are known to be photosensitizers capable of generating radical species. We will synthesize luminescent enantiopure chiral complexes exhibiting CPL, and will examine their ability to transfer polarized electrons. To attain strong CPL and photosensitizing ability, we will target chiral rigid guanidinate ligands. We will also examine the ability of these complexes to transfer polarized electrons and generate polarized radicals with quenching studies of the complexes in their photoexcited states. We will also evaluate the reactivity of polarized radicals toward Csp3-Csp3 cross-coupling reactions using a combination of fluorescence studies and flow chemistry. During the proposed funding period, we expect the delivery of the first examples of CPL-active cerium complex, as well as proof-of-principle for polarized electron transfer. We will also develop early stage proof-of-concept for the polarized radical-based cross-coupling reactions.

概括 该项目的长期目标是发展下一代的跨偶联反应。我们 旨在消除耦合伙伴之间的区分，同时保持高反应性和 通过利用极化激进物种的选择性。我们将利用一个事实，即一个两极分化的激进 物种只会与另一根激进物种反应，其极化。中心假设是 发射强圆极化发光（CPL）具有高能量的配合物 可以收集以进行反应性的极化激子。 CPL是光的发射 极化并已成为下一代光源。灯笼植物络合物是最好的CPL 已知发射剂和瓷器复合物是能够产生激进物种的光敏剂。我们将 合成表现出CPL的发光对映射手性配合物，并将检查其转移能力 偏振电子。为了获得强大的CPL和光敏能力，我们将瞄准手性手性刚性鸟嘌呤 配体。我们还将检查这些配合物传递偏振电子并产生的能力 偏振自由基对其光激发状态中的复合物进行淬灭研究。我们还将评估 极化自由基对CSP3-CSP3交叉偶联反应的反应性，结合了 荧光研究和流动化学。在拟议的资金期间，我们希望第一个交付 CPL活性掌配合物以及极化电子转移的原理证明的示例。我们也会 开发出基于极地自由基的交叉偶联反应的早期概念概念。