Development Novel Photosensitiser Materials Based on Earth-Abundant Elements

开发基于地球丰富元素的新型光敏材料

• 批准号: 2862255
• 金额: --
• 依托单位: University of Huddersfield
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2021
• 资助国家: 英国
• 起止时间: 2021 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2862255
• 关键词: Development; Novel; Photosensitiser; Materials; Based

Photophysical sensitiser materials based on metals such as ruthenium and iridium offer superb performance and avenues for tuning and optimisation of their properties. However, it is a far from simple task to substitute these rare and expensive elements by cheaper and more-abundant first row transition metal elements. The metal-to-ligand charge transfer (MLCT) states that are responsible for the attractive properties of ruthenium(II) d6 complexes are rapidly deactivated in their low-spin d6 iron(II) analogues by metal-centred (MC) states that are much lower lying than for ruthenium and also high-spin states that are inaccessible for ruthenium. A typical approach to remedy this situation has relied upon increasing the donor strength of ligands to increase the d-orbital splitting and raise the energies of these deleterious MC states. However, this approach has only had limited success.In what is a current and extremely hot area in modern inorganic chemistry there has been a move away from attempting to force iron(II) to behave like ruthenium(II) and instead explore alternative electronic configurations of complexes of lighter elements and exploit their own unique photophysical properties. This has led to materials based on d5 Fe(III), d3 Cr(III) and d0 Zr(IV) that exhibit excited states of different electronic character to traditional MLCT states, have record lifetimes and have potent photocatalytic properties.In this project the development of new photosensitiser materials based on lighter Earth-abundant metals will be targeted. This will involve the synthesis of new ligands and their complexes. The photophysical and electrochemical properties of the resultant materials will be thoroughly characterised by steady state methods. In collaboration with world-leading national and international partners materials will also be investigated by ultrafast transient absorption spectroscopy methods with work supported by computational chemistry calculations. Guided by end user needs the synthetic design of complexes will be informed by, and ultimately used to mediate challenging photocatalytic organic transformations and polymerisation reactions.

基于金属（如钌和铱）的光物理感光材料提供了卓越的性能和调整和优化其性能的途径。然而，用更便宜和更丰富的第一行过渡金属元素代替这些稀有和昂贵的元素远非一项简单的任务。金属-配体电荷转移（MLCT）态是钌（II） d6配合物吸引特性的原因，在它们的低自旋d6铁（II）类似物中，金属中心（MC）态比钌低得多，而且高自旋态对钌来说是不可接近的。补救这种情况的一个典型方法是依靠增加配体的供体强度来增加d轨道分裂和提高这些有害MC态的能量。然而，这种方法只取得了有限的成功。在现代无机化学中，这是一个非常热门的领域，人们已经不再试图迫使铁（II）表现得像钌（II）一样，而是探索较轻元素配合物的其他电子构型，并利用它们自己独特的光物理性质。这使得基于d5 Fe(III), d3 Cr（III）和d0 Zr（IV）的材料表现出与传统MLCT状态不同的电子特征激发态，具有创纪录的寿命和强大的光催化性能。在这个项目中，开发基于地球上较轻的金属的新型光敏剂材料将是目标。这将涉及新配体及其配合物的合成。合成材料的光物理和电化学性能将通过稳态方法进行彻底表征。在与世界领先的国家和国际合作伙伴的合作下，材料也将通过计算化学计算支持的超快瞬态吸收光谱方法进行研究。在最终用户需求的指导下，配合物的合成设计将被告知，并最终用于介导具有挑战性的光催化有机转化和聚合反应。