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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:
European Regional Development Fund; European Union (EU); Government of Hungary; Hungarian Academy of Sciences; Icelandic Research Fund; Independent Research Fund Denmark; Knut and Alice Wallenberg Foundation; National Research, Development and Innovation Fund; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
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

References (57)

Vibrational Coherences and Relaxation in the High-Spin State of Aqueous [Fe II (bpy) 3 ] 2+   journal September 2009
Vibrational Coherences and Relaxation in the High-Spin State of Aqueous [Fe II (bpy) 3 ] 2+   journal September 2009
A Heteroleptic Push-Pull Substituted Iron(II) Bis(tridentate) Complex with Low-Energy Charge-Transfer States journal November 2014
A Heteroleptic Ferrous Complex with Mesoionic Bis(1,2,3-triazol-5-ylidene) Ligands: Taming the MLCT Excited State of Iron(II) journal December 2014
Is Iron the New Ruthenium? journal February 2019
N-Heterocyclic Carbene Complexes of Iron as Photosensitizers for Light-Induced Water Reduction: N-Heterocyclic Carbene Complexes of Iron as Photosensitizers for Light-Induced Water Reduction journal March 2017
Global and target analysis of time-resolved spectra journal July 2004
On the role of ligand-field states for the photophysical properties of ruthenium(II) polypyridyl complexes journal January 2015
Spin-state studies with XES and RIXS: From static to ultrafast journal June 2013
Comprehensive data analysis of femtosecond transient absorption spectra: A review journal March 2012
Ultrafast Excited-State Processes in Inorganic Systems journal May 2015
Fe N -Heterocyclic Carbene Complexes as Promising Photosensitizers journal July 2016
Ultrafast Electron Dynamics in Solar Energy Conversion journal May 2017
Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods journal May 2017
Impact of the fac / mer Isomerism on the Excited-State Dynamics of Pyridyl-carbene Fe(II) Complexes journal March 2019
Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering journal February 2016
Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+ journal March 2015
Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer journal January 2019
Fe II Hexa N -Heterocyclic Carbene Complex with a 528 ps Metal-to-Ligand Charge-Transfer Excited-State Lifetime journal January 2018
Mechanistic Studies of Photoinduced Spin Crossover and Electron Transfer in Inorganic Complexes journal March 2015
Synthesis and Characterization of a High-Symmetry Ferrous Polypyridyl Complex: Approaching the 5 T 2 / 3 T 1 Crossing Point for Fe II journal December 2013
Ultrafast Nonadiabatic Dynamics of [Fe II (bpy) 3 ] 2+ in Solution journal July 2007
Experimental Evidence of Ultrafast Quenching of the 3 MLCT Luminescence in Ruthenium(II) Tris-bipyridyl Complexes via a 3 dd State journal September 2013
Photoactive Complexes with Earth-Abundant Metals journal September 2018
Femtochemistry:  Atomic-Scale Dynamics of the Chemical Bond † journal June 2000
Probing the 3d Spin Momentum with X-ray Emission Spectroscopy:  The Case of Molecular-Spin Transitions journal June 2006
Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser: Application to Spin Crossover Dynamics journal January 2013
Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics journal March 2011
Exceptional Excited-State Lifetime of an Iron(II)– N -Heterocyclic Carbene Complex Explained journal May 2014
Tracking excited-state charge and spin dynamics in iron coordination complexes journal May 2014
A low-spin Fe(iii) complex with 100-ps ligand-to-metal charge transfer photoluminescence journal March 2017
Sub-50-fs photoinduced spin crossover in [Fe(bpy)3]2+ journal July 2015
Iron sensitizer converts light to electrons with 92% yield journal October 2015
Coherent structural trapping through wave packet dispersion during photoinduced spin state switching journal May 2017
Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses journal March 2015
Disentangling detector data in XFEL studies of temporally resolved solution state chemistry journal January 2015
A new record excited state 3 MLCT lifetime for metalorganic iron( ii ) complexes journal January 2016
Ultrafast transient IR spectroscopy and DFT calculations of ruthenium( ii ) polypyridyl complexes journal January 2017
Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution journal January 2017
Tracking the picosecond deactivation dynamics of a photoexcited iron carbene complex by time-resolved X-ray scattering journal January 2018
Band-selective dynamics in charge-transfer excited iron carbene complexes journal January 2019
Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy journal January 2019
Towards longer-lived metal-to-ligand charge transfer states of iron(ii) complexes: an N-heterocyclic carbene approach journal January 2013
High sensitivity fluorescence up-conversion spectroscopy of 3 MLCT emission of metal-organic complexes journal January 2019
Structural analysis of ultrafast extended x-ray absorption fine structure with subpicometer spatial resolution: Application to spin crossover complexes journal March 2009
A multi-crystal wavelength dispersive x-ray spectrometer journal July 2012
Low-flux measurements with Cornell's LCLS integrating pixel array detector journal November 2011
Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers journal April 2019
The X-ray Pump–Probe instrument at the Linac Coherent Light Source journal April 2015
Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex journal January 2009
Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime journal November 2018
Electronic structure in the transition metal block and its implications for light harvesting journal January 2019
Iron hits the mark journal January 2019
Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution text January 2017
Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers text January 2019
Photoactive Complexes with Earth-Abundant Metals text January 2018
Is Iron the New Ruthenium? text January 2019

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