Redox-active ligands and their coordination complexes

氧化还原活性配体及其配位化合物

• 批准号: RGPIN-2014-05388
• 负责人: Hicks, Robin
• 金额: $ 3.93万
• 依托单位: University of Victoria
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=653545
• 关键词: Redox; active; ligands; their; coordination

Compounds based on the transition metals are used in an incredibly broad spectrum of applications. They are used as reagents and as catalysts to make new drugs, polymers, and other important classes of chemicals. They also possess physical properties (light absorption, emission, magnetism.) that are exploited in many high-tech applications ranging from MRI to batteries to alternative energy. Whatever the particular application, chemists typically work to tailor the properties of metal complexes by carefully selecting the ligands (or designing new ones) that are bound to the metal. The idea of "ligand design" is endemic to many, many aspects of transition metal chemistry.**By and large these efforts are based on the premise that the properties of metal complexes stem principally from the metal, and the ligands play a supporting role in fine tuning these properties. An alternative approach involves using ligand which themselves have some active function. The ligand property of interest in my research program is redox activity. As their name suggests, "redox-active ligands" (RALs) can be oxidized or reduced analogously to many transition metals. These sorts of ligands have been known for about 50 years but until recently the main focus was on simply trying to understand the electronic structure of RAL complexes. **In the past decade there has been growing recognition that RAL complexes could possess very useful applications: Several technologically important physical properties (optical, magnetic, molecular switching) stem from ligand-based redox activity. And the possibility of harnessing ligand-centered redox activity to make new/more effective/cheaper reagents and catalysts is beginning to receive worldwide attention. These general ideas are still in early stages of exploration; more work is needed to determine the potential uses of RAL complexes.**This proposal outlines research into the synthesis, properties and uses of RAL complexes based on new kinds of redox-active ligands. Other researchers in this field are focusing on well-established types of RALs; my goals are to try to broaden the "RAL toolkit" by developing non-traditional systems under development in my lab. We have discovered two fundamentally new types of redox-active ligand, one based on a class of stable radical and the other based on an industrially important organic dye. Both are straightforward to make, and both have unusual/distinctive properties which can be modulated through conventional substituent effects. The proposed research is principally discovery-oriented, in that we will examine a range of properties for our RAL complexes. This work involves a lot of chemical synthesis (designing and making target molecules, based on hypotheses of what they might "do"). In some cases the "property" is reactivity/catalysis, whereas in others the focus is on electro/optical properties. We will assess the strengths and weaknesses of our systems in relation to other RAL complexes (and more generally, other metal complexes not based on RALs) and in so doing we hope to (i) contribute to the collective understanding of the fundamental nature of redox-active ligands and (ii) identify new opportunities for development in catalysis and/or advanced materials.

基于过渡金属的化合物用于多种应用。它们被用作试剂和催化剂，以制造新药，聚合物和其他重要的化学品类。 它们还具有物理特性（光吸收，发射，磁性。）在许多高科技应用中都利用，从MRI到电池再到替代能量。 无论哪种特定应用，化学家通常都可以通过仔细选择与金属结合的配体（或设计新的）来定制金属配合物的性质。 “配体设计”的想法是过渡金属化学的许多许多方面的特有。另一种方法涉及使用其本身具有某些活动功能的配体。我的研究计划中感兴趣的配体特性是氧化还原活动。顾名思义，可以将“氧化还原活性配体”（RAL）类似地氧化或降低到许多过渡金属。这些配体已经闻名了大约50年，但直到最近，主要重点是简单地试图理解RAL复合物的电子结构。 **在过去的十年中，人们越来越认识到RAL复合物可能具有非常有用的应用：几种在技术上重要的物理特性（光学，磁性，分子切换）源于基于配体的氧化还原活性。以及利用以配体为中心的氧化还原活动的可能性使新/更有效/更便宜的试剂和催化剂开始受到全世界的关注。这些一般思想仍处于探索的早期阶段。需要更多的工作来确定RAL复合物的潜在用途。该领域的其他研究人员正在专注于公认的兰尔类型。我的目标是通过在我的实验室中开发正在开发的非传统系统来扩大“ RAL工具包”。我们已经发现了两种新型的新型氧化还原活性配体，一种基于一类稳定的激进分子，另一种基于工业重要的有机染料。两者都是直接制作的，并且都具有异常/独特的特性，可以通过常规的取代效应来调节。拟议的研究主要以发现为导向，因为我们将研究RAL复合物的一系列特性。这项工作涉及大量的化学合成（根据他们可能“做”的假设设计和制造目标分子）。 在某些情况下，“属性”是反应性/催化，而在其他情况下，重点是电/光学特性。我们将评估系统与其他RAL复合物（以及更普遍的其他金属络合物不是基于鼠标）相关的优势和劣势，因此我们希望（i）（i）有助于集体理解氧化还原活性配体的基本性质，以及（ii）在催化和/或高级材料中确定新的开发机会。