Exploring the light-induced dynamics in solvated metallogrid complexes with femtosecond pulses across the electromagnetic spectrum.
Journaljournal of chemical physics2.991Date
Journal Article
2020-Jun-07 / 152 : 214301
Naumova MA 1, Kalinko A 1, Wong JWL 2, Alvarez Gutierrez S 3, Meng J 3, Liang M 3, Abdellah M 4, Geng H 5, Lin W 4, Kubicek K 6, Biednov M 6, Lima F 6, Galler A 6, Zalden P 6, Checchia S 7, Mante PA 4, Zimara J 8, Schwarzer D 8, Demeshko S 2, Murzin V 1, Gosztola D 9, Jarenmark M 10, Zhang J 11, Bauer M 12, Lawson Daku ML 13, Khakhulin D 6, Gawelda W 6, Bressler C 6, Meyer F 2, Zheng K 3, Canton SE 1
  • 2. Universität Göttingen, Institut für Anorganische Chemie, Tammannstraße 4, 37077 Göttingen, Germany.
  • 3. Department of Chemistry, Technical University of Denmark, DK-2800 Kongens Lyngby, Denmark.
  • 4. Chemical Physics and NanoLund, Lund University, Box 124, 22100 Lund, Sweden.
  • 5. ELI-ALPS, ELI-HU Non-Profit Ltd., Dugonics ter 13, Szeged 6720, Hungary.
  • 6. European XFEL, Holzkoppel 4, 22869 Schenefeld, Germany.
  • 7. MAX IV Laboratory, Lund University, 22100 Lund, Sweden.
  • 8. Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, 37077 Göttingen, Germany.
  • 9. Center for Nanoscale Materials, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, USA.
  • 10. Department of Geology, Lund University, 223 62 Lund, Sweden.
  • 11. State Key Laboratory of Hollow Fiber Membrane Materials and Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China.
  • 12. Department Chemie and Center for Sustainable Systems Design (CSSD), University of Paderborn, Warburger Straße 100, D-33098 Paderborn, Germany.
  • 13. Département de Chimie Physique, Université de Genève, Quai E. Ansermet 30, CH-1211 Genève 4, Switzerland.
Oligonuclear complexes of d4-d7 transition metal ion centers that undergo spin-switching have long been developed for their practical role in molecular electronics. Recently, they also have appeared as promising photochemical reactants demonstrating improved stability. However, the lack of knowledge about their photophysical properties in the solution phase compared to mononuclear complexes is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2 × 2] iron(II) metallogrid complex are characterized by combining measurements with transient optical-infrared absorption and x-ray emission spectroscopy on the femtosecond time scale. The analysis is supported by density functional theory calculations. The photocycle can be described in terms of intra-site transitions, where the FeII centers in the low-spin state are independently photoexcited. The Franck-Condon state decays via the formation of a vibrationally hot high-spin (HS) state that displays coherent behavior within a few picoseconds and thermalizes within tens of picoseconds to yield a metastable HS state living for several hundreds of nanoseconds. Systematic comparison with the closely related mononuclear complex [Fe(terpy)2]2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. More generally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.
J Chem Physjournal of chemical physics
LocationUnited States

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