Simulations on Light-driven Multi-electron-transfer in Artificial Supra-molecular Photocatalysis

• Applicant: Dr. Stephan Kupfer
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation ; Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2020 to 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 448713509

• Final Report Year: 2025

Final Report Abstract

In modern society, humankind has reached a population of approximately 8 billion individuals. To satisfy the ever increasing demand for energy, providing new sources of regenerative energy is of vital importance. A promising source of regenerative energy is sunlight. Different attempts of utilizing solar energy are being pursued, ranging from artificial photosynthesis to direct generation of electricity from solar cells. In this respect, this project aimed to provide novel design strategies for light-harvesting devices and supra-molecular light-driven catalysts in the scope of solar energy conversion and water splitting based on a fully theoretical approach. Therefore, this project employed theoretical and computational methods to design novel photosensitizers (PSs) and supra-molecular photocatalysts (SMPs) with desirable properties and functions. In particular, these systems were designed with the objectives to (i) absorb light in the entire visible region and the near infrared, (ii) store and transfer efficiently multi-electrons to an acceptor site, (iii) reduce charge recombination processes, (iv) display constant properties over a wide range of environmental conditions, and (v) be composed of environmentally friendly and earth-abundant elements (e.g., iron). Although iron-based systems could not be investigated within the scope of this project, the ligand systems developed here led to the development of photoactive iron(II) complexes in a related project (TRR 234 CataLight).

Publications

• Computational Photocatalysis. Bunsen-Magazin, 2023, 6, 200–202.
  S. Kupfer
  
• Cover Feature: Plugging the 3MC Sink in RuII‐Based Photocatalysts (ChemCatChem 4/2023). ChemCatChem, 15(4).
  Shillito, Georgina E.; Rau, Sven & Kupfer, Stephan
  
• Plugging the 3MC Sink in RuII‐Based Photocatalysts. ChemCatChem, 15(4).
  Shillito, Georgina E.; Rau, Sven & Kupfer, Stephan
  
• Stability of Catalytic Centres in Light‐Driven Hydrogen Evolution by Di‐ and Oligonuclear Photocatalysts. Chemistry – A European Journal, 29(36).
  Lämmle, Martin; Mengele, Alexander K.; Shillito, Georgina E.; Kupfer, Stephan & Rau, Sven
  
• The three kingdoms—Photoinduced electron transfer cascades controlled by electronic couplings. The Journal of Chemical Physics, 159(2).
  Yang, Guangjun; Shillito, Georgina E.; Zens, Clara; Dietzek-Ivanšić, Benjamin & Kupfer, Stephan
  
• Controlling Excited State Localization in Bichromophoric Photosensitizers via the Bridging Group. Inorganic Chemistry, 63(11), 4947-4956.
  Shillito, Georgina E.; Preston, Dan; Crowley, James D.; Wagner, Pawel; Harris, Samuel J.; Gordon, Keith C. & Kupfer, Stephan
  
• Steering Photoinduced Electron Transfer in Intramolecular Photocatalysts by Peripheral Ligand Control. ChemistryEurope, 2(6).
  Bagemihl, Benedikt; Müller, Carolin; Shillito, Georgina E.; Hartkorn, Marco; Mengele, Alexander K.; Kupfer, Stephan; Dietzek‐Ivanšić, Benjamin & Rau, Sven
  
• Role of Spacers in Molecularly Linked RuRh Dyads: A Comparative Synthetic and Ultrafast Spectroscopic Investigation. Inorganic Chemistry, 64(15), 7273-7285.
  Semwal, Mohini; Lämmle, Martin; Brohmer, Elias H. P.; Volk, Steffen; Zedler, Linda; Kupfer, Stephan; Mengele, Alexander K.; Shillito, Georgina E.; Rau, Sven & Dietzek-Ivanšić, Benjamin