Leveraging a Tetradentate Redox-active Ligand to Enhance Control Over Properties and Reactivity

利用四齿氧化还原活性配体增强对性质和反应性的控制

• 批准号: 2247241
• 负责人: Alan Heyduk
• 金额: $ 57.5万
• 依托单位: University of California-Irvine
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-09-01 至 2026-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247241&HistoricalAwards=false
• 关键词: Leveraging; Tetradentate; Redox; active; Ligand

With funding from the Chemical Synthesis Program in the Chemistry Division, Professor Alan Heyduk in the Department of Chemistry at the University of California, Irvine will explore the design and synthesis of redox-active ligand platforms that engender improved electronic properties and enhanced reactivity patterns in coordination complexes of transition metal ions. The project is motivated by the fact that the electronic properties and reactivity patterns of coordination complexes play a critical role in diverse areas of research such as the development of new photosensitive materials and the discovery of catalysts for synthesizing fuels and commodity and fine chemicals, respectively. To realize improved electronic properties and enhanced reactivity patterns, the research focuses on new ligand designs that offer tight control over the local coordination environment of the metal ion while also expanding the number of accessible oxidation state available to the metal ion. Collaboration with the SoCal Undergraduate Research Symposium at UCI provides research mentoring and guidance to undergraduate students, many from underrepresented groups, as they prepare to matriculate from graduate degree programs in STEM fields.This project centers on the development of tetradentate, redox-active ligands and the synthesis and characterization of their related transition-metal coordination complexes. The ligand design incorporates an ortho-phenylenediamine backbone that coordinates directly to the metal center and augments metal-based redox process due to its own three oxidation states that are accessible at mild potentials. Additionally, the ligand design incorporates two ancillary “arms” that also bind to the metal ion, providing stability and steric protection at the metal center and offer control over the local coordination environment. These ligand design features are deployed in two thrusts: (a) the development of ligand-to-ligand charge-transfer chromophores and (b) the development of catalysts for multi-electron, atom- and group-transfer reactions. In pursuing this project, the Heyduk group will utilize inorganic synthetic techniques to obtain new molecules for study. New complexes will be characterized by a battery of techniques including electrochemical methods, single crystal X-ray diffraction, NMR, EPR, UV-vis-NIR, and IR spectroscopies, as well as computational methods. Benefits and outcomes of the proposed work include an expanded understanding of how redox-active ligands can be used to control and enhance reactivity at transition metal ions and the training of a workforce skilled in the synthesis, characterization, and utilization of reactive coordination complexes.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

借助化学综合计划的化学分部的资金，加利福尼亚大学化学系的艾伦·海杜克（Alan Heyduk）教授将探索氧化还原活性配体平台的设计和综合，从而促进了改善的电子特性并增强了过渡金属离子配置复合物的反应性模式。该项目的激励是，以下事实：配位复合物的电子特性和反应性模式在研究的潜水区域（例如开发新的光敏感材料的开发以及分别用于合成燃料和成分和细化学物质的催化剂）中起着关键作用。为了实现改进的电子特性和增强的反应性模式，该研究集中于新的配体设计，这些设计可为金属离子的局部协调环境提供严格的控制，同时还扩大了金属离子可访问的氧化状态的数量。与UCI的SOCAL本科研究研讨会的合作为本科生提供了研究心理和指导，其中许多人来自代表性不足的群体，因为他们准备从STEM领域的研究生学位课程中矩阵。该项目集中于四型，氧化还原活性配体的发展，其相关及其相关的综合量为中心。配体设计结合了一个正苯基二胺主链，该主链直接与金属中心协调并增强基于金属的氧化还原工艺，这是由于其自身在轻度电势下可访问的氧化状态。此外，配体设计结合了两个辅助“臂”，它们也与金属离子结合，在金属中心提供稳定性和空间保护，并提供对当地协调环境的控制。这些配体设计特征分为两个推力：（a）配体 - 配体电荷转移发色团的发展，以及（b）多电子，原子和组转移反应的催化剂的开发。在追求该项目时，Heyduk组将利用无机合成技术来获得新的研究分子。新的复合物将以一系列技术为特征，包括电化学方法，单晶X射线衍射，NMR，EPR，UV-VIS-NIR和IR光谱镜以及计算方法。拟议工作的益处和结果包括对如何使用氧化还原活性的配体来控制和增强过渡金属离子的反应性以及对熟练的劳动力的培训，这些劳动力熟练在综合，表征和利用中的反应性协调综合体中，这种奖项反映了NSF的法定任务和审查的范围，这是通过评估的范围来评估的。