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Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy

Journal Article · · Angewandte Chemie (International Edition)
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  1. Lund Univ. (Sweden)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  3. Technical Univ. of Denmark, Lyngby (Denmark)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Technical Univ. of Denmark, Lyngby (Denmark)
  5. Hungarian Academy of Sciences, Budapest (Hungary)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  8. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  9. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); ELI-HU Non-Profit Ltd., Szeged (Hungary)
  10. Technical Univ. of Denmark, Lyngby (Denmark); Univ. of Iceland, Reykjavik (Iceland)
+ Show Author Affiliations

Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. Here, we present a sub-ps X-ray spectroscopy study of an FeIINHC complex that identifies absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3MLCT state, from the initially excited 1MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3MC state, in comand quantifies the states involved in the deactivation cascade after light petition with vibrational relaxation and cooling to the relaxed 3MLCT state. The relaxed 3MLCT state then decays much more slowly (7.6 ps) to the 3MC state. The 3MC state is rapidly (2.2 ps) deactivated to the ground state. The 5MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Independent Research Fund Denmark; Icelandic Research Fund; European Union (EU); European Regional Development Fund; Hungarian Academy of Sciences; Government of Hungary; National Research, Development and Innovation Fund; Knut and Alice Wallenberg Foundation
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1633958
Alternate ID(s):
OSTI ID: 1572578
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 1 Vol. 59; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems journal May 2008
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering text January 2020
Design and Synthesis of Photoactive Iron N-Heterocyclic Carbene Complexes journal January 2020

Figures / Tables (8)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
X-ray spectroscopy
femtochemistry molecular dynamics
photochemistry
photophysics