Müller Carolin, Schwab Alexander, Randell Nicholas M, Kupfer Stephan, Dietzek-Ivanšić Benjamin, Chavarot-Kerlidou Murielle
Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743, Jena, Germany.
Research Department Functional Interfaces, Leibniz Institute of Photonic Technology Jena, Albert-Einstein-Straße 9, 07745, Jena, Germany.
Chemistry. 2022 Mar 28;28(18):e202103882. doi: 10.1002/chem.202103882. Epub 2022 Mar 8.
The design of photoactive systems capable of storing and relaying multiple electrons is highly demanded in the field of artificial photosynthesis, where transformations of interest rely on multielectronic redox processes. The photophysical properties of the ruthenium photosensitizer [(bpy) Ru(oxim-dppqp)] (Ru), storing two electrons coupled to two protons on the π-extended oxim-dppqp ligand under light-driven conditions, are investigated by means of excitation wavelength-dependent resonance Raman and transient absorption spectroscopies, in combination with time-dependent density functional theory; the results are discussed in comparison to the parent [(bpy) Ru(dppz)] and [(bpy) Ru(oxo-dppqp)] complexes. In addition, this study provides in-depth insights on the impact of protonation or of accumulation of multiple reducing equivalents on the reactive excited states.
在人工光合作用领域，对能够存储和传递多个电子的光活性系统的设计有很高的需求，因为该领域中感兴趣的转化过程依赖于多电子氧化还原过程。通过激发波长相关的共振拉曼光谱和瞬态吸收光谱，并结合含时密度泛函理论，研究了钌光敏剂[(bpy)Ru(oxim-dppqp)]（Ru）在光驱动条件下在π-扩展的肟-dppqp配体上存储两个与两个质子耦合的电子的光物理性质；并与母体[(bpy)Ru(dppz)]和[(bpy)Ru(oxo-dppqp)]配合物进行对比讨论了结果。此外，本研究还深入探讨了质子化或多个还原当量的积累对反应性激发态的影响。
