Thermal and photochemical assembly of light-harvesting complexes: an electrochemical, optical and computational investigation.

光捕获复合物的热和光化学组装：电化学、光学和计算研究。

• 批准号: 203301-2013
• 负责人: Hanan, Garry
• 金额: $ 6.12万
• 依托单位: Université de Montréal
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2015
• 资助国家: 加拿大
• 起止时间: 2015-01-01 至 2016-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=569923
• 关键词: Thermal; photochemical; assembly; light; harvesting

Solar energy conversion of light into chemical energy offers humankind the possibility to forgo our current dependence on fossil fuels. This step forward towards alternative energy would curb global warming and guarantee a cleaner environment for future generations. In this Discovery Grant application, I propose to mimic natural photosynthesis using coordination and supramolecular chemistry to assemble light-harvesting complexes capable of capturing sunlight over most of the visible spectrum. We also propose to use a new synthetic methodology based on photochemical irradiation to produce our oligo- and poly-metallic light-harvesting complexes. This new approach is based on the fact that light excitation of metal-ligand bonds can in some instances break these bonds. By careful design and synthesis of ligands we can dictate which bonds will break and which bonds will not in any given metal complex. For example, bi- and tri-dentate ligands are more stable than mono-dentate ligands due to the chelate effect. By incorporating all three types of ligands into the same complex, we can push photoreactions towards the ejection of the mono-dentate ligand only. Indeed, careful design can even dictate the loss of one particular mono-dentate ligand over another. The self-assembly of squares, hexagons and octagons containing metal ions such as Ru, Pt, Re and Ir is envisaged. These multimetallic complexes will be photochemically assembled and examined by electrochemical and spectroscopic experiments to fully understand their fundamental properties. They will then be included into photocatalytic systems to examine the production of chemical energy. New Co-catalysts will allow us to produce dihydrogen from water. A new instrumental technique was developed in my group which will allow us to monitor the UV-visible absorption spectroscopy of the photoreaction while we monitor dihydrogen production. This powerful new technique will allow us to probe deeper into the catalytic cycle and develop the next generation of photocatalysts and light-harvesting complexes.

光能将光转化为化学能提供了人类的可能性，可以放弃我们目前对化石燃料的依赖。朝着替代能源迈进的这一步将遏制全球变暖，并确保为子孙后代提供更清洁的环境。在此发现赠款应用中，我建议使用协调和超分子化学反应模仿自然光合作用，以组装能够在大多数可见光谱上捕获阳光的轻度收获复合物。我们还建议使用基于光化学辐照的新合成方法来产生我们的寡质和多金属轻料复合物。这种新方法是基于以下事实：在某些情况下，金属配体键的光激发可以打破这些键。通过仔细的设计和配体的合成，我们可以决定哪些键将断裂，哪些键在任何给定的金属配合物中都不会。例如，由于螯合作用，双配体和三齿配体比单态配体更稳定。通过将所有三种类型的配体掺入同一复合物中，我们只能将光反应朝向单丁二酸配体的射击。确实，仔细的设计甚至可以决定一种特定的单一牙配体的损失，而不是另一种。设想了含有RU，PT，RE和IR等金属离子的正方形，六角形和八块的自组装。这些多功能复合物将通过电化学和光谱实验对光化学组装和检查，以充分了解其基本特性。然后，它们将被纳入光催化系统中，以检查化学能的产生。新的共催化剂将使我们能够从水中产生二氢。在我的小组中开发了一种新的仪器技术，这将使我们能够监测二氢生产时光电反应的紫外可见吸收光谱。这项强大的新技术将使我们能够深入探测催化循环，并发展下一代的光催化剂和轻度收获的复合物。