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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

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Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution text January 2017
Femtosecond Absorption Spectroscopy of Transition Metal Charge-Transfer Complexes journal March 2004
Vibrational Coherences and Relaxation in the High-Spin State of Aqueous [Fe II (bpy) 3 ] 2+   journal September 2009
Ultrafast Deactivation Mechanism of the Excited Singlet in the Light-Induced Spin Crossover of [Fe(2,2′-bipyridine) 3 ] 2+ journal November 2013
On the role of the metal-to-ligand charge transfer states in the light-induced spin crossover in FeII (bpy)3 journal February 2011
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information journal January 2005
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
High-Efficiency Iron Photosensitizer Explained with Quantum Wavepacket Dynamics journal May 2016
Mechanistic Studies of Photoinduced Spin Crossover and Electron Transfer in Inorganic Complexes journal March 2015
New Photosensitizers Based upon [Fe(L) 2 (CN) 2 ] and [Fe(L) 3 ] (L = Substituted 2,2‘-Bipyridine):  Yields for the Photosensitization of TiO 2 and Effects on the Band Selectivity journal April 2000
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Electronic absorption spectra of the iron(II) complexes of 2,2'-bipyridine, 2,2'-bipyrimidine, 1,10-phenanthroline, and 2,2':6',2''-terpyridine and their reduction products journal February 1992
Charge-Transfer Studies of Iron Cyano Compounds Bound to Nanocrystalline TiO 2 Surfaces journal March 2002
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
Engineering of Efficient Panchromatic Sensitizers for Nanocrystalline TiO 2 -Based Solar Cells journal February 2001
Highly Phosphorescent Bis-Cyclometalated Iridium Complexes:  Synthesis, Photophysical Characterization, and Use in Organic Light Emitting Diodes journal May 2001
Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion journal September 1982
Lifetimes, spectra, and quenching of the excited states of polypyridine complexes of iron(II), ruthenium(II), and osmium(II) journal February 1980
Mixed Ligand Complexes of Iron(II) and (III) with Cyanide and Aromatic Di-imines journal June 1960
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
Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency
  • Pollock, Christopher J.; Delgado-Jaime, Mario Ulises; Atanasov, Mihail
  • Journal of the American Chemical Society, Vol. 136, Issue 26 https://doi.org/10.1021/ja504182n
journal June 2014
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
Femtosecond Excited-State Dynamics of an Iron(II) Polypyridyl Solar Cell Sensitizer Model journal May 2000
Highly Strained Iron(II) Polypyridines: Exploiting the Quintet Manifold To Extend the Lifetime of MLCT Excited States journal February 2016
Probing the 3d Spin Momentum with X-ray Emission Spectroscopy:  The Case of Molecular-Spin Transitions journal June 2006
Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics journal March 2011
Coherent structural trapping through wave packet dispersion during photoinduced spin state switching journal May 2017
Towards longer-lived metal-to-ligand charge transfer states of iron(ii) complexes: an N-heterocyclic carbene approach journal January 2013
Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex journal January 2009

Cited By (16)

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
Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer journal July 2019
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
Improving the Light-Induced Spin Transition Efficiency in Ni(II)-Based Macrocyclic-Ligand Complexes journal November 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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