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

Journal Article · · Structural Dynamics
DOI:https://doi.org/10.1063/1.4985017· OSTI ID:1362282
 [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)
+ Show Author Affiliations

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.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515; AMOS program within the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Ba
OSTI ID:
1362282
Alternate ID(s):
OSTI ID: 1366564
Journal Information:
Structural Dynamics, Vol. 4, Issue 4; ISSN 2329-7778
Publisher:
American Crystallographic Association/AIPCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science

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  • Journal of the American Chemical Society, Vol. 136, Issue 26 https://doi.org/10.1021/ja504182n
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Cited By (13)

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
Toward Luminescent Iron Complexes: Unravelling the Photophysics by Computing Potential Energy Surfaces journal May 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
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
Ab initio study of ultrafast laser-induced spin flip, spin-flip transfer, and spin crossover in Co m Bz n + / 0 clusters ( m , n = 1 , 2 ) journal September 2018
A high-throughput energy-dispersive tender X-ray spectrometer for shot-to-shot sulfur measurements journal April 2019
Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime journal November 2018
NHC-Based Iron Sensitizers for DSSCs journal June 2018
Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes journal November 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
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering text January 2020
Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer other January 2019

Figures / Tables (6)

FIG. 1(p. 4)figure FIG. 1
FIG. 2(p. 5)figure FIG. 2
FIG. 3(p. 6)figure FIG. 3
FIG. 4(p. 7)figure FIG. 4
FIG. 5(p. 8)figure FIG. 5
TABLE 1(p. 9)table TABLE 1

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