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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 3 d 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:
Journal Article: 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 = {Thu Jul 06 00:00:00 EDT 2017},
month = {Thu Jul 06 00:00:00 EDT 2017}
}

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Works referenced in this record:

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