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: 2016
• 资助国家: 加拿大
• 起止时间: 2016-01-01 至 2017-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=613601
• 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.

在我的小组中进行的研究，通过NSERC加拿大研究主席的支持，重点是制备新的“响应”有机材料，其中的物理（磁）特性响应于周围环境的变化，如热，光或压力。在过去的几年里，我们在这一领域的研究已经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。我们通过这项发现补助金寻求资金，以更充分地探索化学的这些新领域。虽然我们可以预见这项研究在中长期内产生的潜在利益，但目前应用的目标是充分发展基础化学，以便我们能够在适当的时候利用科学。 项目1.在过去的4年里，我们开发了合成方法，以获得一系列被称为噻二嗪的有机分子，作为我们CRC资助的材料化学计划的构建模块。然而，这些分子的核心结构也是一系列噻嗪类药物的核心，这些药物可用于治疗高血压和骨质疏松症等疾病。这两类化合物之间的显着差异是有机分子中硫原子的“氧化态”，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的一系列过渡金属的配位化学。这是以前从未尝试过的，所得的配合物具有潜在的不同性质，从新的磁性材料到光致发光器件和催化剂。我们将系统地探索这个新的化合物家族的化学和材料特性。 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个被称为四硫辛的分子家族，我们可以很容易地生产出数克的数量。在过去的几年中，我们发现这些四硫辛可以与选定的金属（镍，钯和铂）反应，形成“金属二硫代物”。这些二硫代化合物在生物学中作为金属酶的模型，在材料化学中作为磁体，导体，光学材料和太阳能电池中进行了广泛的研究。我们的合成方法提供了一个令人兴奋的机会，只需1-2步即可获得新的二硫代化合物家族，这些化合物提供了潜在的增强电子性能，例如更有效的太阳能电池染料。 因此，该应用包括两个不同的研究项目，它们不仅有助于科学知识，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的出色培训，这将直接使加拿大市场受益。