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Title: Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+

Journal Article · · Journal of Physical Chemistry. C
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  1. Hungarian Academy Sciences, Budapest (Hungary)
  2. Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Physics
  3. European Synchrotron Radiation Facility (ESRF), Cedex (France)
  4. Argonne National Lab., IL (United States). Advanced Photon Source
  5. European XFEL, Hamburg (Germany)
  6. Sorbonne Universites - UPMC Univ. Paris (France)
  7. SLAC National Accelerator Center, Menlo Park, CA (United States)
  8. Lund Univ. (Sweden). Dept. of Chemical Physics
+ Show Author Affiliations

Theoretical predictions show that depending on the populations of the Fe 3dxy, 3dxz, and 3dyz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)2]2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy)2]2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy)2]2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe–ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)–high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1208941
Journal Information:
Journal of Physical Chemistry. C, Vol. 119, Issue 11; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 64 works
Citation information provided by
Web of Science

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Boosting Vis/NIR Charge-Transfer Absorptions of Iron(II) Complexes by N-Alkylation and N-Deprotonation in the Ligand Backbone journal May 2017
Structural Dynamics of Spin Crossover in Iron(II) Complexes with Extended-Tripod Ligands journal September 2017
Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy journal October 2019
Time-resolved X-ray spectroscopies of chemical systems: New perspectives journal May 2016
Spin-state dependence of the structural and vibrational properties of solvated iron( ii ) polypyridyl complexes from AIMD simulations: II. aqueous [Fe(tpy) 2 ]Cl 2 journal January 2019
Structural Dynamics of Spin Crossover in Iron(II) Complexes with Extended-Tripod Ligands text January 2017
Theoretical X‐ray spectroscopy of transition metal compounds journal July 2019
Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)$_5$ via a singlet pathway upon excitation at 266 nm text January 2017
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Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity journal October 2019
Toward Luminescent Iron Complexes: Unravelling the Photophysics by Computing Potential Energy Surfaces journal May 2019
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On the calculation of x-ray scattering signals from pairwise radial distribution functions journal November 2015
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Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy journal January 2020
A multi-MHz single-shot data acquisition scheme with high dynamic range: pump–probe X-ray experiments at synchrotrons journal October 2016
X-ray Absorption and Emission Spectroscopic Studies of [L 2 Fe 2 S 2 ] n Model Complexes: Implications for the Experimental Evaluation of Redox States in Iron–Sulfur Clusters journal April 2016

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