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Title: Exploring the Light-induced Dynamics in Solvated Metallogrid Complexes with Femtosecond Pulses Across the Electromagnetic Spectrum

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5138641· OSTI ID:1712729
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  1. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  2. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Univ. of Paderborn (Germany)
  3. Univ. Goettingen (Germany)
  4. Technical Univ. of Denmark, Lyngby (Denmark)
  5. Lund Univ. (Sweden)
  6. ELI-HU Non-Profit Ltd., Szeged (Hungary)
  7. European X-ray Free-Electron Laser (XFEL), Schenefeld (Germany)
  8. Lund Univ. (Sweden); Hong Kong Polytechnic Univ., Kowloon (Hong Kong)
  9. Max Planck Inst. for Biophysical Chemistry, Göttingen (Germany)
  10. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Bergische Univ., Wuppertal (Germany)
  11. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  12. Tianjin Polytechnic Univ., Xiqing (China)
  13. Univ. of Paderborn (Germany)
  14. Univ. of Geneva (Switzerland)
  15. European X-ray Free-Electron Laser (XFEL), Schenefeld (Germany); Adam Mickiewicz Univ., Poznan (Poland)
  16. European X-ray Free-Electron Laser (XFEL), Schenefeld (Germany); Univ. of Hamburg (Germany)
  17. Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ. (Sweden)
  18. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); ELI-HU Non-Profit Ltd., Szeged (Hungary)
+ Show Author Affiliations

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 their mononuclear congeners is currently hampering their inclusion into advanced light-driven reactions. In the present study, the ultrafast photoinduced dynamics in a solvated [2x2] iron(II) metallogrid complex are characterized by combining transient optical, infrared absorption and X-ray emission spectroscopic measurements on the femtosecond timescale. The analysis is supported by DFT calculations. The photocycle can be described in terms of intra-site transitions, where the FeII in the low-spin (LS) 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 picosecond to yield a metastable HS state living for several hundreds of nanoseconds. Additionally, systematic comparison with the closely related mononuclear complex [Fe(terpy)2]2+ reveals that nuclearity has a profound impact on the photoinduced dynamics. Finally, this work provides guidelines for expanding the integration of oligonuclear complexes into new photoconversion schemes that may be triggered by ultrafast spin-switching.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Office of Basic Energy Sciences (BES); European XFEL; German Research Foundation (DFG); Chinese Scholarship Council; German Federal Ministry of Education and Research (BMBF); Polish National Science Centre (NCN); Hamburg Centre for Ultrafast Imaging; French National Research Agency (ANR); European Regional Development Fund (ERDF)
Grant/Contract Number:
AC02-06CH11357; 05K18PPA; 05K19PP1; BA-4467/7-1; 2016/22/E/ST4/00543; 2.3.6-15-2015-00001
OSTI ID:
1712729
Alternate ID(s):
OSTI ID: 1631383
Journal Information:
Journal of Chemical Physics, Vol. 152, Issue 21; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
absorption spectroscopy
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