Light-driven electron and energy transfer in metallocorrole complexes: A combined femtosecond visible/IR and nanosecond EPR investigation

金属咔络合物中的光驱动电子和能量转移：飞秒可见光/红外和纳秒 EPR 组合研究

• 批准号: 69343136
• 负责人: Professor Dr. Karsten Heyne
• 金额: --
• 依托单位: Institut für Experimentalphysik
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2008
• 资助国家: 德国
• 起止时间: 2007-12-31 至 2013-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/69343136?language=en
• 关键词: Light; driven; electron; energy; transfer

Corroles, a rapidly developing class of tetrapyrroles, retain the aromatic character of porphyrins but differ by their ability to accommodate metals in higher oxidation states, and thus exhibit exceptional photophysical and chemical properties, relevant to basic science as well as technological applications. In this research proposal we concentrate on the influence of the core metal ion and axial ligands on photophysical and photochemical processes in the metallocorroles, and corrole based donor-acceptor complexes. The focus will be on metallocorroles with Al(lll), Ga(lll), Sb(lll), or Sb(V) as the central metal ion, covering the range from light to fairly heavy metal ions, and allowing the study of the influence of the oxidation state. The kinetics and structural dynamics of newly synthesized metallocorroles will be characterized on femtosecond to millisecond timescales, using polarizationresolved femtosecond visible and infrared spectroscopy, multimode electron paramagnetic resonance (EPR), and laser flash photolysis. The impact of the core metal ion and its oxidation states on the 3-dimensional structure will be studied. The results on isolated metallocorroles will be implemented in studies of photoinduced electron and energy transfer in corrole based donor-acceptor complexes. Particular emphasis will be devoted to the dependence of electron and energy transfer on the donor-acceptor distance, their mutual orientation, and the nature of their linkage such as covalent, electrostatic, coordinative, and hydrogen bonding. The information gained will enhance the development of advanced catalytic processes and the design of efficient biomimetic systems.

咔咯是一种快速发展的四吡咯类化合物，它保留了卟啉的芳香特性，但不同之处在于它们容纳更高氧化态金属的能力，因此表现出与基础科学以及技术应用相关的特殊物理和化学性质。在这项研究中，我们集中在核心金属离子和轴向配体的影响，在金属corroles，和corrole为基础的供体-受体配合物的物理和光化学过程。重点将放在金属腐蚀与铝（III），镓（III），锑（III），或锑（V）作为中心金属离子，覆盖范围从轻到相当重的金属离子，并允许研究的氧化态的影响。新合成的metalcorroles的动力学和结构动力学的特点是在飞秒到毫秒的时间尺度上，使用polarizationresolved飞秒可见光和红外光谱，多模电子顺磁共振（EPR），和激光闪光光解。将研究核心金属离子及其氧化态对三维结构的影响。对孤立金属配合物的研究结果将应用于基于咔咯的给体-受体配合物中光诱导电子和能量转移的研究。特别强调将致力于电子和能量转移的供体-受体的距离，它们的相互取向，以及它们的连接，如共价键，静电键，配位键和氢键的性质的依赖。所获得的信息将促进先进催化工艺的开发和高效仿生系统的设计。