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Title: Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN)4]2-

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI: https://doi.org/10.1039/c7cp07838b · OSTI ID:1426489
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  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). PULSE Institute; Technical University of Denmark, Lyngby (Denmark). Molecular Movies, Department of Physics; Lund Univ. (Sweden). Department of Chemical Physics
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). PULSE Institute
  3. Technical University of Denmark, Lyngby (Denmark). Molecular Movies, Department of Physics; Lund Univ. (Sweden). Department of Chemical Physics
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). LCLS
  5. Technical University of Denmark, Lyngby (Denmark). Molecular Movies, Department of Physics
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). PULSE Institute; Technical University of Denmark, Lyngby (Denmark). Molecular Movies, Department of Physics
  7. Lund Univ. (Sweden). Department of Chemical Physics
  8. Lund Univ. (Sweden). Department of Chemical Physics and Centre for Analysis and Synthesis, Department of Chemistry
  9. Hungarian Academy of Sciences, Budapest (Hungary). Wigner Research Centre for Physics
  10. SLAC National Accelerator Lab., Menlo Park, CA (United States). SSRL
  11. SLAC National Accelerator Lab., Menlo Park, CA (United States). LCLS; SwissFEL, Paul Scherrer Institut, Villigen (Switzerland)
  12. ELI-ALPS, ELI-HU Non-Profit Ltd. (Hungary); FS-ATTO, Deutsches Elektronen-Synchrotron (DESY ), Hamburg (Germany)
  13. Lund Univ. (Sweden). Centre for Analysis and Synthesis, Department of Chemistry
  14. Lund Univ. (Sweden). Theoretical Chemistry Division
  15. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). PULSE Institute and SSRL
+ Show Author Affiliations

The excited state dynamics of solvated [Fe(bpy)(CN)4]2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN)4]2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile. Here, in the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN)4]2- in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet (3MC) character, unlike other reported six-coordinate Fe(II)-centered coordination compounds, which form MC quintet (5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN)4]2- allows us to infer the influence of the solvent on the electronic structure of the complex. Lastly, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1426489
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 6 Vol. 20; ISSN 1463-9076; ISSN PPCPFQ
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (68)

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
The Role of Ligand-Field States in the Ultrafast Photophysical Cycle of the Prototypical Iron(II) Spin-Crossover Compound [Fe(ptz) 6 ](BF 4 ) 2 journal March 2014
Ultrafast Deactivation Mechanism of the Excited Singlet in the Light-Induced Spin Crossover of [Fe(2,2′-bipyridine) 3 ] 2+ journal November 2013
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
Ultrafast Spin Crossover in [Fe II (bpy) 3 ] 2+ : Revealing Two Competing Mechanisms by Extreme Ultraviolet Photoemission Spectroscopy journal January 2017
An Iron-Based Photosensitizer with Extended Excited-State Lifetime: Photophysical and Photovoltaic Properties: An Iron-Based Photosensitizer with Extended Excited-State Lifetime journal April 2015
On the role of the metal-to-ligand charge transfer states in the light-induced spin crossover in FeII (bpy)3 journal February 2011
First-Row Transition Metal Complexes for the Conversion of Light into Electricity and Electricity into Light book January 2015
Ruthenium-Based Photosensitizers for Dye-Sensitized Solar Cells book January 2015
Spectroscopic studies of preferential and asymmetric solvation in substituted cyanoiron(II) complexes journal August 1983
Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence journal March 1988
Structural and electronic responses of coordination compounds to changes in the molecule and molecular environment journal July 1992
Ultrafast mid-IR detection of the direct precursor to the presolvated electron following electron ejection from ferrocyanide journal October 2000
Bis(1,10-phenanthroline) dicyanoiron(II): an almost universal inorganic solvent polarity indicator journal March 1990
Mechanism of photoinduced redox reactions in aqueous solutions of [Fe(bpy)(CN)4]2− journal January 1991
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information journal January 2005
Light-induced spin crossover in Fe(II)-based complexes: The full photocycle unraveled by ultrafast optical and X-ray spectroscopies journal November 2010
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
Fe N -Heterocyclic Carbene Complexes as Promising Photosensitizers journal July 2016
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
Effect of tert -Butyl Functionalization on the Photoexcited Decay of a Fe(II)- N -Heterocyclic Carbene Complex journal July 2016
High-Efficiency Iron Photosensitizer Explained with Quantum Wavepacket Dynamics journal May 2016
High-Resolution X-ray Emission and X-ray Absorption Spectroscopy journal June 2001
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
The (N 4 C 2 ) 2– Donor Set as Promising Motif for Bis(tridentate) Iron(II) Photoactive Compounds journal November 2013
Solvatochromic and Ionochromic Effects of Iron(II)bis(1,10-phenanthroline)dicyano: a Theoretical Study journal February 2010
Design of Long-Lived Ru(II) Terpyridine MLCT States. Tricyano Terpyridine Complexes journal November 1998
Subpicosecond 1MLCT .fwdarw. 5T2 intersystem crossing of low-spin polypyridyl ferrous complexes journal January 1993
Solvent tuning of the excited-state properties of (2,2'-bipyridine)tetracyanoferrate(II): direct observation of a metal-to-ligand charge-transfer excited state of iron(II) journal May 1987
Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion (Ru(bpy)32+). Solvent effects journal August 1983
A 3.0 μs Room Temperature Excited State Lifetime of a Bistridentate Ru II −Polypyridine Complex for Rod-like Molecular Arrays journal October 2006
Ultrafast Nonadiabatic Dynamics of [Fe II (bpy) 3 ] 2+ in Solution journal July 2007
Probing Valence Orbital Composition with Iron Kβ X-ray Emission Spectroscopy journal July 2010
Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy journal May 2010
Bis(tridentate) Ruthenium–Terpyridine Complexes Featuring Microsecond Excited-State Lifetimes journal July 2012
Direct Probing of Spin State Dynamics Coupled with Electronic and Structural Modifications by Picosecond Time-Resolved XAFS journal January 2010
Femtosecond Excited-State Dynamics of an Iron(II) Polypyridyl Solar Cell Sensitizer Model journal May 2000
Photoaquation Mechanism of Hexacyanoferrate(II) Ions: Ultrafast 2D UV and Transient Visible and IR Spectroscopies journal May 2017
Picosecond X-ray Absorption Spectroscopy of a Photoinduced Iron(II) Spin Crossover Reaction in Solution journal January 2006
Probing the 3d Spin Momentum with X-ray Emission Spectroscopy:  The Case of Molecular-Spin Transitions journal June 2006
Solvent Dependence of Absorption and Emission Spectra of Ru(bpy) 2 (CN) 2 :  Experiment and Explanation Based on Electronic Structure Theory journal December 2007
Guest–Host Interactions Investigated by Time-Resolved X-ray Spectroscopies and Scattering at MHz Rates: Solvation Dynamics and Photoinduced Spin Transition in Aqueous Fe(bipy) 3 2+ journal October 2012
Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser: Application to Spin Crossover Dynamics journal January 2013
X-ray Spectroscopic Study of Solvent Effects on the Ferrous and Ferric Hexacyanide Anions journal September 2014
Influence of Solvent on the Spectroscopic Properties of Cyano Complexes of Ruthenium(II) journal January 1996
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
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
Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses journal March 2015
Spectroelectrochemical identification of charge-transfer excited states in transition metal-based polypyridyl complexes journal January 2014
Reversing the relative 3 MLCT– 3 MC order in Fe( ii ) complexes using cyclometallating ligands: a computational study aiming at luminescent Fe( ii ) complexes journal January 2015
A new record excited state 3 MLCT lifetime for metalorganic iron( ii ) complexes journal January 2016
Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution journal January 2017
Towards longer-lived metal-to-ligand charge transfer states of iron(ii) complexes: an N-heterocyclic carbene approach journal January 2013
A multi-crystal wavelength dispersive x-ray spectrometer journal July 2012
Photooxidation and photoaquation of iron hexacyanide in aqueous solution: A picosecond X-ray absorption study journal March 2014
Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine) 2 (CN) 2 ] journal July 2017
Low-flux measurements with Cornell's LCLS integrating pixel array detector journal November 2011
Photon-in photon-out hard X-ray spectroscopy at the Linac Coherent Light Source journal April 2015
The X-ray Pump–Probe instrument at the Linac Coherent Light Source journal April 2015
Femtosecond Dynamics of Excited-State Evolution in [Ru(bpy)3]2+ journal January 1997
Monitoring Excited State Charge Transfer of Transition Metal Mixed-Valence Complexes with Femtosecond X-ray Absorption and Emission Spectroscopy conference January 2016
Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution text January 2017

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Kovalenzgetriebene Erhaltung lokaler Ladungsdichten in einem durch Metall‐Ligand‐Ladungstransfer angeregten Eisenphotosensibilisator journal July 2019
Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer journal July 2019
Towards Noble-Metal-Free Dyads: Ground and Excited State Tuning by a Cobalt Dimethylglyoxime Motif Connected to an Iron N-Heterocyclic Carbene Photosensitizer: Towards Noble-Metal-Free Dyads: Ground and Excited State Tuning by a Cobalt Dimethylglyoxime Motif Connected to an Iron N-Heterocyclic Carbene Photose journal December 2018
Photophysical properties of bichromophoric Fe(II) complexes bearing an aromatic electron acceptor journal June 2019
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe( ii ) complexes journal January 2018
Excited-state solvation structure of transition metal complexes from molecular dynamics simulations and assessment of partial atomic charge methods journal January 2019
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
Hole dynamics in a photovoltaic donor-acceptor couple revealed by simulated time-resolved X-ray absorption spectroscopy journal July 2019
Simulation of ultrafast excited-state dynamics and elastic x-ray scattering by quantum wavepacket dynamics journal September 2019
Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity journal October 2019
Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers journal April 2019
Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers text January 2019
Hole dynamics in a photovoltaic donor-acceptor couple revealed by simulated time-resolved X-ray absorption spectroscopy text January 2019
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering text January 2020
NHC-Based Iron Sensitizers for DSSCs journal June 2018
Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer other January 2019
Excited-State Solvation Structure of Transition Metal Complexes from Molecular Dynamics Simulations and Assessment of Partial Atomic Charge Methods text January 2018

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14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY