A Spectroscopic Investigation of Luminescent Cr(III) Complexes

发光 Cr(III) 配合物的光谱研究

• 批准号: 2269243
• 金额: --
• 依托单位: CARDIFF UNIVERSITY
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2019
• 资助国家: 英国
• 起止时间: 2019 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2269243
• 关键词: Spectroscopic; Investigation; Luminescent; Cr; III

Photochemistry, in which visible or ultraviolet light is used as a catalyst to promote the formation of new chemical species with distinct chemical properties, is of growing importance for molecular synthesis, therapeutic diagnostics and new technological applications such as light emitting diodes. Absorption of light energy frequently involves the creation of paramagnetic excited states or charge carriers that play vital roles in electron transfer events, displaying significantly different chemistry to ground state processes. However, these species often evade detection due to their incredibly short lifetimes. In this project we will apply TR-EPR methods to yield accurate resolution of kinetics, molecular profiles, and structural models which cannot be accessed under steady-state conditions due to rapid relaxation processes. TR-EPR will provide fundamental knowledge of charge transport mechanisms required for the optimization of efficient photosynthetic systems and devices. This research is directly relevant to EPSRC Strategic Priority for Photonic Materials and the related Materials for Energy Applications themes.This project will provide a Ph.D. training regimen in advanced spectroscopy and chemical synthesis, in a collaborative nature between an experienced project team. Two areas of initial research activity will focus on (i) Photon Upconversion by Ir(III) Complexes, and (ii) Sustainable sensitizers for dye-sensitized semiconductor solar cells. Both research areas will yield significant advances within the project timeframe.Photon upconversion has received significant attention as a means of increasing the efficacy of light harvesting processes, photoredox catalysis and for bioimaging agents. The Co-I has recently demonstrated leading conversion efficiencies using novel Ir(III)-based donor:acceptor systems through triplet-triplet upconversion (Chem. Eur. J. (2018), DOI:10.1002/chem.201801007). TR-EPR is ideally suited to fully disentangle the spin interactions of the photoexcited system (e.g. transient organic triplets, spin-orbit coupling parameters), results guiding rational design of donor:acceptor pairs for maximum upconversion and selective emission wavelengths. Photoexcitation of metal oxide semiconductors creates charge carriers that can be utilised in surface redox processes and in electrical thin-film devices. The PI has recently provided unique insights into this area by utilising EPR to identify intrinsic/dopant oxidation state changes during photoirradiation. The development of copper-based sensitizers (by the Co-I) will be explored to maximise photoexcitation profiles and optimise charge-transfer processes providing a sustainable, low-cost route towards solar cells of the future.

光化学，其中可见光或紫外光被用作催化剂以促进具有独特化学性质的新化学物种的形成，对于分子合成、治疗诊断和新技术应用（例如发光二极管）具有日益重要的意义。光能的吸收通常涉及顺磁激发态或电荷载流子的产生，这些顺磁激发态或电荷载流子在电子转移事件中起重要作用，显示出与基态过程显著不同的化学性质。然而，这些物种往往由于其令人难以置信的短寿命而逃避检测。在这个项目中，我们将应用TR-EPR方法来产生动力学，分子概况和结构模型的准确分辨率，这些模型由于快速弛豫过程而无法在稳态条件下访问。TR-EPR将提供优化高效光合系统和设备所需的电荷传输机制的基础知识。该研究与EPSRC光子材料战略优先级和相关的能源应用材料主题直接相关。高级光谱学和化学合成的培训方案，在经验丰富的项目团队之间的协作性质。初步研究活动的两个领域将集中在（i）Ir（III）络合物的光子上转换，以及（ii）染料敏化半导体太阳能电池的可持续敏化剂。这两个研究领域都将在项目时间范围内取得重大进展。光子上转换作为提高光捕获过程、光氧化还原催化和生物成像剂效率的一种手段，受到了极大的关注。Co-I最近已经证明了使用新的基于Ir（III）的供体：受体系统通过三重态-三重态上转换的领先的转换效率（Chem.Eur. J.（2018），DOI：10.1002/chem.201801007）。TR-EPR非常适合于完全解开光激发系统的自旋相互作用（例如瞬态有机三重态，自旋轨道耦合参数），结果指导合理设计供体：受体对以获得最大上转换和选择性发射波长。金属氧化物半导体的光激发产生可用于表面氧化还原过程和电薄膜器件的电荷载流子。PI最近提供了独特的见解到这一领域，利用EPR来确定内在/掺杂剂的氧化态变化在光照射。将探索铜基敏化剂（由Co-I开发）的开发，以最大限度地提高光激发曲线并优化电荷转移过程，为未来的太阳能电池提供可持续的低成本路线。