Redox Active Heterocycles: From Free Radicals to Non-Innocent Ligands

氧化还原活性杂环：从自由基到非无辜配体

• 批准号: RGPIN-2015-05523
• 负责人: Rawson, Jeremy
• 金额: $ 2.55万
• 依托单位: University of Windsor
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2019
• 资助国家: 加拿大
• 起止时间: 2019-01-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=685898
• 关键词: Redox; Active; Heterocycles; Free; Radicals

The research undertaken in my group, supported through an NSERC Canada Research Chair, has focused on preparing new 'responsive' organic materials in which the physical (magnetic) properties respond to changes in the surroundings such as heat, light or pressure. During the last few years our research in this area has uncovered several new areas of coordination chemistry which are not directly related to our research on organic materials but provide exciting opportunities to open up new avenues of research. We seek funding through this Discovery Grant to more fully explore these new areas of chemistry. Whilst we can foresee potential benefits arising from this research in the medium-long term, the objective of the current application is to fully develop the underpinning chemistry in order that we can position ourselves to exploit the science in the fullness of time.***Project 1. In the last 4 years we have developed synthetic methodologies to access a range of organic molecules known as thiadiazines as building blocks in our CRC-funded materials chemistry program. However the core structure of these molecules is also central to a series of thiazide drugs which have applications in treating medical conditions such as hypertension and osteoporosis. The significant difference between these two classes of compound is the "oxidation state" of the sulphur atom in the organic molecules which substantially changes their electronic properties. In this project we aim to explore the coordination chemistry of these thiadiazines to a range of transition metals. This has never been attempted previously and the resultant complexes have potentially diverse properties ranging from new magnetic materials to photo-luminescent devices and catalysts. We will systematically explore the chemistry and materials properties of this new family of compounds.****Project 2. A key intermediate in some of our magnetic-materials research is a family of molecules known as tetrathiocines which we can readily generate in multi-gram quantities. In the past few years we have found these tetrathiocines can react with selected metals (nickel, palladium and platinum) to form 'metal dithiolates'. These dithiolate compounds are studied extensively in biology as models for metallo-enzymes and in materials chemistry as magnets, conductors, optical materials and in solar cells. Our synthetic methodology provides an exciting opportunity to access new families of dithiolate complexes in just 1-2 steps which offer potentially enhanced electronic properties such as more efficient dyes for solar cells.***This application thus comprises two distinct research programs which will not only contribute to scientific knowledge, but may offer potential applications in molecular materials science and will provide excellent training of next-generation HQP which will directly benefit the Canadian market place.*** **

在我的团队中进行的这项研究，在NSERC加拿大研究主席的支持下，专注于制备新的有机材料，这些材料的物理(磁性)性质对环境的变化(如热、光或压力)做出反应。在过去的几年里，我们在这一领域的研究发现了几个新的配位化学领域，这些领域与我们对有机材料的研究没有直接关系，但为开辟新的研究途径提供了令人兴奋的机会。我们通过这项发现赠款寻求资金，以更充分地探索这些化学新领域。虽然我们可以预见这项研究在中长期内产生的潜在好处，但当前应用的目标是充分开发基础化学，以便我们能够在充分的时间内定位自己开发这项科学。*项目1。在过去的4年中，我们开发了合成方法来访问一系列有机分子，称为噻二氮，作为我们CRC资助的材料化学计划的构建块。然而，这些分子的核心结构也是一系列噻嗪类药物的核心，这些药物在治疗高血压和骨质疏松等医疗疾病方面有应用。这两类化合物之间的显著区别是有机分子中硫原子的“氧化状态”，这大大改变了它们的电子性质。在这个项目中，我们的目标是探索这些噻二嗪与一系列过渡金属的配位化学。这是以前从未尝试过的，所得到的络合物具有潜在的不同的性质，从新的磁性材料到光致发光设备和催化剂。我们将系统地探索这一新的化合物家族的化学和材料性质。*项目2。在我们的一些磁性材料研究中，一个关键的中间体是一种被称为四硫代辛的分子家族，我们可以很容易地产生多克量的四硫代辛。在过去的几年里，我们发现这些四硫杂环己烷可以与选定的金属(镍、钯和铂)反应，形成“金属二硫代硫酸盐”。这些二硫化合物作为金属酶的模型在生物学中被广泛研究，在材料化学中作为磁铁、导体、光学材料和太阳能电池中被广泛研究。我们的合成方法提供了一个令人兴奋的机会，只需1-2步就可以获得新的二硫化合物家族，从而提供潜在的增强的电子性能，例如用于太阳能电池的更高效的染料。*因此，这一应用包括两个不同的研究计划，这不仅将有助于科学知识，而且可能在分子材料科学中提供潜在的应用，并将提供对下一代HQP的优秀培训，这将直接使加拿大市场受益。*