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Title: Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine)2(CN)2]

Abstract

Here, we have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy)2(CN)2], where bpy=2,2'-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2'-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy)2(CN)2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a short lived metal-centered triplet transient species. These measurements of [Fe(bpy)2(CN)2] complement prior measurement performed on [Fe(bpy)3]2+ and [Fe(bpy)(CN)4]2– in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy)N(CN)6–2N]2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3d transition metal complexes.

Authors:
 [1];  [2];  [3];  [4];  [3];  [5];  [6];  [7];  [3];  [8];  [3];  [6];  [9];  [10];  [3];  [11];  [3];  [12];  [13];  [3] more »;  [9];  [9];  [9];  [14] « less
  1. Stanford Univ., Menlo Park, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ., Lund (Sweden)
  2. Stanford Univ., Menlo Park, CA (United States); Beijing Normal Univ., Beijing (China)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Stanford Univ., Menlo Park, CA (United States)
  5. Stanford Univ., Stanford, CA (United States)
  6. Stanford Univ., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  7. Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ., Lund (Sweden)
  8. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Max Planck Institute for Biophysical Chemistry, Gottingen (Germany)
  9. Lund Univ., Lund (Sweden)
  10. Technical Univ. of Denmark, Lyngby (Denmark)
  11. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  12. Technical Univ. of Denmark, Lyngby (Denmark); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  13. HPSTAR, Shanghai (China)
  14. Stanford Univ., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1362282
Alternate Identifier(s):
OSTI ID: 1366564
Grant/Contract Number:  
AC02-76SF00515; AMOS program within the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Ba
Resource Type:
Accepted Manuscript
Journal Name:
Structural Dynamics
Additional Journal Information:
Journal Volume: 4; Journal Issue: 4; Journal ID: ISSN 2329-7778
Publisher:
American Crystallographic Association/AIP
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Kjaer, Kasper S., Zhang, Wenkai, Alonso-Mori, Roberto, Bergmann, Uwe, Chollet, Matthieu, Hadt, Ryan G., Hartsock, Robert W., Harlang, Tobias, Kroll, Thomas, Kubicek, Katharina, Lemke, Henrik T., Liang, Huiyang W., Liu, Yizhu, Nielsen, Martin M., Robinson, Joseph S., Solomon, Edward I., Sokaras, Dimosthenis, van Driel, Tim B., Weng, Tsu -Chien, Zhu, Diling, Persson, Petter, Warnmark, Kenneth, Sundstrom, Villy, and Gaffney, Kelly J. Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine)2(CN)2]. United States: N. p., 2017. Web. doi:10.1063/1.4985017.
Kjaer, Kasper S., Zhang, Wenkai, Alonso-Mori, Roberto, Bergmann, Uwe, Chollet, Matthieu, Hadt, Ryan G., Hartsock, Robert W., Harlang, Tobias, Kroll, Thomas, Kubicek, Katharina, Lemke, Henrik T., Liang, Huiyang W., Liu, Yizhu, Nielsen, Martin M., Robinson, Joseph S., Solomon, Edward I., Sokaras, Dimosthenis, van Driel, Tim B., Weng, Tsu -Chien, Zhu, Diling, Persson, Petter, Warnmark, Kenneth, Sundstrom, Villy, & Gaffney, Kelly J. Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine)2(CN)2]. United States. doi:10.1063/1.4985017.
Kjaer, Kasper S., Zhang, Wenkai, Alonso-Mori, Roberto, Bergmann, Uwe, Chollet, Matthieu, Hadt, Ryan G., Hartsock, Robert W., Harlang, Tobias, Kroll, Thomas, Kubicek, Katharina, Lemke, Henrik T., Liang, Huiyang W., Liu, Yizhu, Nielsen, Martin M., Robinson, Joseph S., Solomon, Edward I., Sokaras, Dimosthenis, van Driel, Tim B., Weng, Tsu -Chien, Zhu, Diling, Persson, Petter, Warnmark, Kenneth, Sundstrom, Villy, and Gaffney, Kelly J. Thu . "Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine)2(CN)2]". United States. doi:10.1063/1.4985017. https://www.osti.gov/servlets/purl/1362282.
@article{osti_1362282,
title = {Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine)2(CN)2]},
author = {Kjaer, Kasper S. and Zhang, Wenkai and Alonso-Mori, Roberto and Bergmann, Uwe and Chollet, Matthieu and Hadt, Ryan G. and Hartsock, Robert W. and Harlang, Tobias and Kroll, Thomas and Kubicek, Katharina and Lemke, Henrik T. and Liang, Huiyang W. and Liu, Yizhu and Nielsen, Martin M. and Robinson, Joseph S. and Solomon, Edward I. and Sokaras, Dimosthenis and van Driel, Tim B. and Weng, Tsu -Chien and Zhu, Diling and Persson, Petter and Warnmark, Kenneth and Sundstrom, Villy and Gaffney, Kelly J.},
abstractNote = {Here, we have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy)2(CN)2], where bpy=2,2'-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2'-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy)2(CN)2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a short lived metal-centered triplet transient species. These measurements of [Fe(bpy)2(CN)2] complement prior measurement performed on [Fe(bpy)3]2+ and [Fe(bpy)(CN)4]2– in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy)N(CN)6–2N]2N-4, where N = 1–3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3d transition metal complexes.},
doi = {10.1063/1.4985017},
journal = {Structural Dynamics},
number = 4,
volume = 4,
place = {United States},
year = {2017},
month = {7}
}

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Works referenced in this record:

Medium Effects on Charge Transfer in Metal Complexes
journal, June 1998

  • Chen, Pingyun; Meyer, Thomas J.
  • Chemical Reviews, Vol. 98, Issue 4
  • DOI: 10.1021/cr941180w

Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser: Application to Spin Crossover Dynamics
journal, January 2013

  • Lemke, Henrik T.; Bressler, Christian; Chen, Lin X.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 4
  • DOI: 10.1021/jp312559h

Femtosecond Absorption Spectroscopy of Transition Metal Charge-Transfer Complexes
journal, December 2003

  • McCusker, James K.
  • Accounts of Chemical Research, Vol. 36, Issue 12
  • DOI: 10.1021/ar030111d

Ultrafast Nonadiabatic Dynamics of [Fe II (bpy) 3 ] 2+ in Solution
journal, July 2007

  • Gawelda, Wojciech; Cannizzo, Andrea; Pham, Van-Thai
  • Journal of the American Chemical Society, Vol. 129, Issue 26
  • DOI: 10.1021/ja070454x

Probing the 3d Spin Momentum with X-ray Emission Spectroscopy:  The Case of Molecular-Spin Transitions
journal, June 2006

  • Vankó, György; Neisius, Thomas; Molnár, Gábor
  • The Journal of Physical Chemistry B, Vol. 110, Issue 24
  • DOI: 10.1021/jp0615961

Lifetimes, spectra, and quenching of the excited states of polypyridine complexes of iron(II), ruthenium(II), and osmium(II)
journal, February 1980

  • Creutz, Carol; Chou, Mei; Netzel, Thomas L.
  • Journal of the American Chemical Society, Vol. 102, Issue 4
  • DOI: 10.1021/ja00524a014

High-Efficiency Iron Photosensitizer Explained with Quantum Wavepacket Dynamics
journal, May 2016

  • Pápai, Mátyás; Vankó, György; Rozgonyi, Tamás
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 11
  • DOI: 10.1021/acs.jpclett.6b00711

Study of the Light-Induced Spin Crossover Process of the [Fe II (bpy) 3 ] 2+ Complex
journal, April 2010

  • de Graaf, Coen; Sousa, Carmen
  • Chemistry - A European Journal, Vol. 16, Issue 15
  • DOI: 10.1002/chem.200903423

A new record excited state 3 MLCT lifetime for metalorganic iron( ii ) complexes
journal, January 2016

  • Liu, Li; Duchanois, Thibaut; Etienne, Thibaud
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 18
  • DOI: 10.1039/C6CP01418F

Probing Valence Orbital Composition with Iron Kβ X-ray Emission Spectroscopy
journal, July 2010

  • Lee, Nicole; Petrenko, Taras; Bergmann, Uwe
  • Journal of the American Chemical Society, Vol. 132, Issue 28
  • DOI: 10.1021/ja101281e

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching
journal, May 2017

  • Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15342

Highly Strained Iron(II) Polypyridines: Exploiting the Quintet Manifold To Extend the Lifetime of MLCT Excited States
journal, February 2016

  • Shepard, Samuel G.; Fatur, Steven M.; Rappé, Anthony K.
  • Journal of the American Chemical Society, Vol. 138, Issue 9
  • DOI: 10.1021/jacs.5b13524

Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex
journal, January 2009


Vibrational Coherences and Relaxation in the High-Spin State of Aqueous [Fe II (bpy) 3 ] 2+
journal, September 2009

  • Consani, Cristina; Prémont-Schwarz, Mirabelle; ElNahhas, Amal
  • Angewandte Chemie International Edition, Vol. 48, Issue 39
  • DOI: 10.1002/anie.200902728

Lifetimes and spectra of the excited states of cis-dicyanobis(2,2'-bipyridine)iron(II) and -ruthenium(II) in solution
journal, January 1987

  • Winkler, Jay R.; Sutin, Norman
  • Inorganic Chemistry, Vol. 26, Issue 2
  • DOI: 10.1021/ic00249a003

Engineering of Efficient Panchromatic Sensitizers for Nanocrystalline TiO 2 -Based Solar Cells
journal, February 2001

  • Nazeeruddin, Mohammad K.; Péchy, Peter; Renouard, Thierry
  • Journal of the American Chemical Society, Vol. 123, Issue 8
  • DOI: 10.1021/ja003299u

On the interplay between charge, spin and structural dynamics in transition metal complexes
journal, January 2012


Tracking excited-state charge and spin dynamics in iron coordination complexes
journal, May 2014

  • Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe
  • Nature, Vol. 509, Issue 7500
  • DOI: 10.1038/nature13252

Highly Phosphorescent Bis-Cyclometalated Iridium Complexes:  Synthesis, Photophysical Characterization, and Use in Organic Light Emitting Diodes
journal, May 2001

  • Lamansky, Sergey; Djurovich, Peter; Murphy, Drew
  • Journal of the American Chemical Society, Vol. 123, Issue 18
  • DOI: 10.1021/ja003693s

Photosensitization of TiO 2 by [Fe II (2,2‘-bipyridine-4,4‘-dicarboxylic acid) 2 (CN) 2 ]:  Band Selective Electron Injection from Ultra-Short-Lived Excited States
journal, February 1998

  • Ferrere, Suzanne; Gregg, Brian A.
  • Journal of the American Chemical Society, Vol. 120, Issue 4
  • DOI: 10.1021/ja973504e

Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution
journal, January 2017

  • Zhang, Wenkai; Kjær, Kasper S.; Alonso-Mori, Roberto
  • Chemical Science, Vol. 8, Issue 1
  • DOI: 10.1039/C6SC03070J

Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency
journal, June 2014

  • Pollock, Christopher J.; Delgado-Jaime, Mario Ulises; Atanasov, Mihail
  • Journal of the American Chemical Society, Vol. 136, Issue 26
  • DOI: 10.1021/ja504182n

High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information
journal, January 2005


Sub-50-fs photoinduced spin crossover in [Fe(bpy)3]2+
journal, July 2015

  • Auböck, Gerald; Chergui, Majed
  • Nature Chemistry, Vol. 7, Issue 8
  • DOI: 10.1038/nchem.2305

Isomerization Through Conical Intersections
journal, May 2007


On the role of the metal-to-ligand charge transfer states in the light-induced spin crossover in FeII (bpy)3
journal, February 2011

  • Graaf, Coen De; Sousa, Carmen
  • International Journal of Quantum Chemistry, Vol. 111, Issue 13
  • DOI: 10.1002/qua.22991

Ultrafast Deactivation Mechanism of the Excited Singlet in the Light-Induced Spin Crossover of [Fe(2,2′-bipyridine) 3 ] 2+
journal, November 2013

  • Sousa, Carmen; de Graaf, Coen; Rudavskyi, Andrii
  • Chemistry - A European Journal, Vol. 19, Issue 51
  • DOI: 10.1002/chem.201302992

Triplet photosensitizers: from molecular design to applications
journal, January 2013

  • Zhao, Jianzhang; Wu, Wanhua; Sun, Jifu
  • Chemical Society Reviews, Vol. 42, Issue 12
  • DOI: 10.1039/c3cs35531d

Spin-state studies with XES and RIXS: From static to ultrafast
journal, June 2013

  • Vankó, György; Bordage, Amélie; Glatzel, Pieter
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 188
  • DOI: 10.1016/j.elspec.2012.09.012

Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion
journal, September 1982

  • Durham, Bill; Caspar, Jonathan V.; Nagle, Jeffrey K.
  • Journal of the American Chemical Society, Vol. 104, Issue 18
  • DOI: 10.1021/ja00382a012

Femtosecond Excited-State Dynamics of an Iron(II) Polypyridyl Solar Cell Sensitizer Model
journal, May 2000

  • Monat, Jeremy E.; McCusker, James K.
  • Journal of the American Chemical Society, Vol. 122, Issue 17
  • DOI: 10.1021/ja992436o

Mechanistic Studies of Photoinduced Spin Crossover and Electron Transfer in Inorganic Complexes
journal, March 2015

  • Zhang, Wenkai; Gaffney, Kelly J.
  • Accounts of Chemical Research, Vol. 48, Issue 4
  • DOI: 10.1021/ar500407p

Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics
journal, March 2011

  • Huse, Nils; Cho, Hana; Hong, Kiryong
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 8
  • DOI: 10.1021/jz200168m

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

  • Winkler, Jay R.; Creutz, Carol; Sutin, Norman
  • Journal of the American Chemical Society, Vol. 109, Issue 11
  • DOI: 10.1021/ja00245a053

High-Resolution X-ray Emission and X-ray Absorption Spectroscopy
journal, June 2001


Spectroscopic studies of preferential and asymmetric solvation in substituted cyanoiron(II) complexes
journal, August 1983

  • Toma, Henrique E.; Takasugi, Maria S.
  • Journal of Solution Chemistry, Vol. 12, Issue 8
  • DOI: 10.1007/BF01150847

Towards longer-lived metal-to-ligand charge transfer states of iron(ii) complexes: an N-heterocyclic carbene approach
journal, January 2013

  • Liu, Yizhu; Harlang, Tobias; Canton, Sophie E.
  • Chemical Communications, Vol. 49, Issue 57
  • DOI: 10.1039/c3cc43833c

Energy-dispersive X-ray emission spectroscopy using an X-ray free-electron laser in a shot-by-shot mode
journal, November 2012

  • Alonso-Mori, R.; Kern, J.; Gildea, R. J.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 47, p. 19103-19107
  • DOI: 10.1073/pnas.1211384109

Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated [ Co ( terpy ) 2 ] 2 +
journal, June 2016


Fe N -Heterocyclic Carbene Complexes as Promising Photosensitizers
journal, July 2016


Mixed Ligand Complexes of Iron(II) and (III) with Cyanide and Aromatic Di-imines
journal, June 1960

  • Schilt, Alfred A.
  • Journal of the American Chemical Society, Vol. 82, Issue 12
  • DOI: 10.1021/ja01497a007

Charge-Transfer Studies of Iron Cyano Compounds Bound to Nanocrystalline TiO 2 Surfaces
journal, March 2002

  • Yang, Mei; Thompson, David W.; Meyer, Gerald J.
  • Inorganic Chemistry, Vol. 41, Issue 5
  • DOI: 10.1021/ic011069q

A low-spin Fe(iii) complex with 100-ps ligand-to-metal charge transfer photoluminescence
journal, March 2017

  • Chábera, Pavel; Liu, Yizhu; Prakash, Om
  • Nature, Vol. 543, Issue 7647
  • DOI: 10.1038/nature21430

    Works referencing / citing this record:

    Ligand manipulation of charge transfer excited state relaxation and spin crossover in $\mathrm{[Fe(2,2′-bipyridine)_{2}(CN)_{2}]}$
    text, January 2017

    • Kjær, Kasper S.; Zhang, Wenkai; Alonso-Mori, Roberto
    • Deutsches Elektronen-Synchrotron, DESY, Hamburg
    • DOI: 10.3204/pubdb-2018-01464

    Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime
    journal, November 2018


    Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer
    journal, July 2019

    • Jay, Raphael M.; Eckert, Sebastian; Vaz da Cruz, Vinícius
    • Angewandte Chemie International Edition, Vol. 58, Issue 31
    • DOI: 10.1002/anie.201904761

    Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer
    journal, July 2019

    • Jay, Raphael M.; Eckert, Sebastian; Vaz da Cruz, Vinícius
    • Angewandte Chemie International Edition, Vol. 58, Issue 31
    • DOI: 10.1002/anie.201904761

    Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime
    journal, November 2018