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

四吡咯是一类发展迅速的四吡咯，它保留了卟啉的芳香性，但不同于它们在更高的氧化态下容纳金属的能力，因此表现出特殊的光物理和化学性质，与基础科学和技术应用有关。在这项研究方案中，我们集中在核心金属离子和轴向配体对金属配位和基于考拉尔的给体-受体络合物中光物理和光化学过程的影响。重点将放在以Al(111)、Ga(111)、Sb(111)或Sb(V)为中心金属离子的金属配位角色上，涵盖从轻到相当重金属离子的范围，并允许研究氧化态的影响。利用偏振分辨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，将在飞秒到毫秒的时间尺度上表征新合成的金属配位的动力学和结构动力学。将研究核心金属离子及其氧化态对三维结构的影响。有关孤立金属配位的结果将应用于基于钴的给体-受体络合物中的光致电子和能量转移的研究。将特别强调电子和能量转移对施主-受主距离的依赖、它们的相互取向以及它们的连接的性质，如共价键、静电键、配位键和氢键。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。

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.