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

Kjær, Kasper S.; Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe; Chollet, Matthieu; Hadt, Ryan G.; Hartsock, Robert W.; Harlang, Tobias; Kroll, Thomas; Kubiček, 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; Wärnmark, Kenneth; Sundström, Villy; Gaffney, Kelly J.

doi:10.1063/1.4985017

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

Journal Article · 06 June 2017 · Structural Dynamics

DOI: https://doi.org/10.1063/1.4985017 · OSTI ID:2565105

Kjær, Kasper S.; Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe; Chollet, Matthieu; Hadt, Ryan G.; Hartsock, Robert W.; Harlang, Tobias; Kroll, Thomas; Kubiček, 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 more »

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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AMOS program within the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Ba; AC02-76SF00515

OSTI ID:: 2565105

Alternate ID(s):: OSTI ID: 1362282; OSTI ID: 1366564

Journal Information:: Structural Dynamics, Journal Name: Structural Dynamics Vol. 4 Journal Issue: 4; ISSN 2329-7778

Publisher:: American Institute of PhysicsCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Medium Effects on Charge Transfer in Metal Complexes Chen, Pingyun; Meyer, Thomas J. Chemical Reviews, Vol. 98, Issue 4 https://doi.org/10.1021/cr941180w	journal	June 1998
Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser: Application to Spin Crossover Dynamics Lemke, Henrik T.; Bressler, Christian; Chen, Lin X. The Journal of Physical Chemistry A, Vol. 117, Issue 4 https://doi.org/10.1021/jp312559h	journal	January 2013
Femtosecond Absorption Spectroscopy of Transition Metal Charge-Transfer Complexes McCusker, James K. Accounts of Chemical Research, Vol. 36, Issue 12 https://doi.org/10.1021/ar030111d	journal	December 2003
Ultrafast Nonadiabatic Dynamics of [Fe ^II (bpy) ₃ ] ²⁺ in Solution Gawelda, Wojciech; Cannizzo, Andrea; Pham, Van-Thai Journal of the American Chemical Society, Vol. 129, Issue 26 https://doi.org/10.1021/ja070454x	journal	July 2007
Probing the 3d Spin Momentum with X-ray Emission Spectroscopy: The Case of Molecular-Spin Transitions Vankó, György; Neisius, Thomas; Molnár, Gábor The Journal of Physical Chemistry B, Vol. 110, Issue 24 https://doi.org/10.1021/jp0615961	journal	June 2006
Lifetimes, spectra, and quenching of the excited states of polypyridine complexes of iron(II), ruthenium(II), and osmium(II) Creutz, Carol; Chou, Mei; Netzel, Thomas L. Journal of the American Chemical Society, Vol. 102, Issue 4 https://doi.org/10.1021/ja00524a014	journal	February 1980
High-Efficiency Iron Photosensitizer Explained with Quantum Wavepacket Dynamics Pápai, Mátyás; Vankó, György; Rozgonyi, Tamás The Journal of Physical Chemistry Letters, Vol. 7, Issue 11 https://doi.org/10.1021/acs.jpclett.6b00711	journal	May 2016
Study of the Light-Induced Spin Crossover Process of the [Fe ^II (bpy) ₃ ] ²⁺ Complex de Graaf, Coen; Sousa, Carmen Chemistry - A European Journal, Vol. 16, Issue 15 https://doi.org/10.1002/chem.200903423	journal	April 2010
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 Braterman, Paul S.; Song, Jae Inh; Peacock, Robert D. Inorganic Chemistry, Vol. 31, Issue 4 https://doi.org/10.1021/ic00030a006	journal	February 1992
A new record excited state ³ MLCT lifetime for metalorganic iron( ii ) complexes Liu, Li; Duchanois, Thibaut; Etienne, Thibaud Physical Chemistry Chemical Physics, Vol. 18, Issue 18 https://doi.org/10.1039/C6CP01418F	journal	January 2016
Probing Valence Orbital Composition with Iron Kβ X-ray Emission Spectroscopy Lee, Nicole; Petrenko, Taras; Bergmann, Uwe Journal of the American Chemical Society, Vol. 132, Issue 28 https://doi.org/10.1021/ja101281e	journal	July 2010
Spectroelectrochemistry of aromatic ligands and their derivatives. 1. Reduction products of 4,4'-bipyridine, 2,2'-bipyridine, 2,2'-bipyrimidine, and some quaternized derivatives Braterman, Paul S.; Song, Jae Inh The Journal of Organic Chemistry, Vol. 56, Issue 15 https://doi.org/10.1021/jo00015a021	journal	July 1991
Coherent structural trapping through wave packet dispersion during photoinduced spin state switching Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15342	journal	May 2017
Highly Strained Iron(II) Polypyridines: Exploiting the Quintet Manifold To Extend the Lifetime of MLCT Excited States Shepard, Samuel G.; Fatur, Steven M.; Rappé, Anthony K. Journal of the American Chemical Society, Vol. 138, Issue 9 https://doi.org/10.1021/jacs.5b13524	journal	February 2016
Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex Bressler, Ch.; Milne, C.; Pham, V. -T. Science, Vol. 323, Issue 5913 https://doi.org/10.1126/science.1165733	journal	January 2009
Vibrational Coherences and Relaxation in the High-Spin State of Aqueous [Fe ^II (bpy) ₃ ] ²⁺ Consani, Cristina; Prémont-Schwarz, Mirabelle; ElNahhas, Amal Angewandte Chemie International Edition, Vol. 48, Issue 39 https://doi.org/10.1002/anie.200902728	journal	September 2009
Lifetimes and spectra of the excited states of cis-dicyanobis(2,2'-bipyridine)iron(II) and -ruthenium(II) in solution Winkler, Jay R.; Sutin, Norman Inorganic Chemistry, Vol. 26, Issue 2 https://doi.org/10.1021/ic00249a003	journal	January 1987
Engineering of Efficient Panchromatic Sensitizers for Nanocrystalline TiO ₂ -Based Solar Cells Nazeeruddin, Mohammad K.; Péchy, Peter; Renouard, Thierry Journal of the American Chemical Society, Vol. 123, Issue 8 https://doi.org/10.1021/ja003299u	journal	February 2001
On the interplay between charge, spin and structural dynamics in transition metal complexes Chergui, Majed Dalton Transactions, Vol. 41, Issue 42 https://doi.org/10.1039/c2dt30764b	journal	January 2012
Tracking excited-state charge and spin dynamics in iron coordination complexes Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe Nature, Vol. 509, Issue 7500 https://doi.org/10.1038/nature13252	journal	May 2014
Highly Phosphorescent Bis-Cyclometalated Iridium Complexes: Synthesis, Photophysical Characterization, and Use in Organic Light Emitting Diodes Lamansky, Sergey; Djurovich, Peter; Murphy, Drew Journal of the American Chemical Society, Vol. 123, Issue 18 https://doi.org/10.1021/ja003693s	journal	May 2001
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 Ferrere, Suzanne Chemistry of Materials, Vol. 12, Issue 4 https://doi.org/10.1021/cm990713k	journal	April 2000
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 Ferrere, Suzanne; Gregg, Brian A. Journal of the American Chemical Society, Vol. 120, Issue 4 https://doi.org/10.1021/ja973504e	journal	February 1998
Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution Zhang, Wenkai; Kjær, Kasper S.; Alonso-Mori, Roberto Chemical Science, Vol. 8, Issue 1 https://doi.org/10.1039/C6SC03070J	journal	January 2017
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
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information Glatzel, Pieter; Bergmann, Uwe Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.04.011	journal	January 2005
[8] Singular value decomposition: Application to analysis of experimental data Henry, E. R.; Hofrichter, J. Methods in Enzymology https://doi.org/10.1016/0076-6879(92)10010-B	book	January 1992
Sub-50-fs photoinduced spin crossover in [Fe(bpy)3]2+ Auböck, Gerald; Chergui, Majed Nature Chemistry, Vol. 7, Issue 8 https://doi.org/10.1038/nchem.2305	journal	July 2015
Isomerization Through Conical Intersections Levine, Benjamin G.; Martínez, Todd J. Annual Review of Physical Chemistry, Vol. 58, Issue 1 https://doi.org/10.1146/annurev.physchem.57.032905.104612	journal	May 2007
On the role of the metal-to-ligand charge transfer states in the light-induced spin crossover in FeII (bpy)3 Graaf, Coen De; Sousa, Carmen International Journal of Quantum Chemistry, Vol. 111, Issue 13 https://doi.org/10.1002/qua.22991	journal	February 2011
Ultrafast Deactivation Mechanism of the Excited Singlet in the Light-Induced Spin Crossover of [Fe(2,2′-bipyridine) ₃ ] ²⁺ Sousa, Carmen; de Graaf, Coen; Rudavskyi, Andrii Chemistry - A European Journal, Vol. 19, Issue 51 https://doi.org/10.1002/chem.201302992	journal	November 2013
Triplet photosensitizers: from molecular design to applications Zhao, Jianzhang; Wu, Wanhua; Sun, Jifu Chemical Society Reviews, Vol. 42, Issue 12 https://doi.org/10.1039/c3cs35531d	journal	January 2013
Spin-state studies with XES and RIXS: From static to ultrafast Vankó, György; Bordage, Amélie; Glatzel, Pieter Journal of Electron Spectroscopy and Related Phenomena, Vol. 188 https://doi.org/10.1016/j.elspec.2012.09.012	journal	June 2013
Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion Durham, Bill; Caspar, Jonathan V.; Nagle, Jeffrey K. Journal of the American Chemical Society, Vol. 104, Issue 18 https://doi.org/10.1021/ja00382a012	journal	September 1982
Femtosecond Excited-State Dynamics of an Iron(II) Polypyridyl Solar Cell Sensitizer Model Monat, Jeremy E.; McCusker, James K. Journal of the American Chemical Society, Vol. 122, Issue 17 https://doi.org/10.1021/ja992436o	journal	May 2000
Mechanistic Studies of Photoinduced Spin Crossover and Electron Transfer in Inorganic Complexes Zhang, Wenkai; Gaffney, Kelly J. Accounts of Chemical Research, Vol. 48, Issue 4 https://doi.org/10.1021/ar500407p	journal	March 2015
Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics Huse, Nils; Cho, Hana; Hong, Kiryong The Journal of Physical Chemistry Letters, Vol. 2, Issue 8 https://doi.org/10.1021/jz200168m	journal	March 2011
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) Winkler, Jay R.; Creutz, Carol; Sutin, Norman Journal of the American Chemical Society, Vol. 109, Issue 11 https://doi.org/10.1021/ja00245a053	journal	May 1987
High-Resolution X-ray Emission and X-ray Absorption Spectroscopy de Groot, Frank Chemical Reviews, Vol. 101, Issue 6 https://doi.org/10.1021/cr9900681	journal	June 2001
Spectroscopic studies of preferential and asymmetric solvation in substituted cyanoiron(II) complexes Toma, Henrique E.; Takasugi, Maria S. Journal of Solution Chemistry, Vol. 12, Issue 8 https://doi.org/10.1007/BF01150847	journal	August 1983
Towards longer-lived metal-to-ligand charge transfer states of iron(ii) complexes: an N-heterocyclic carbene approach Liu, Yizhu; Harlang, Tobias; Canton, Sophie E. Chemical Communications, Vol. 49, Issue 57 https://doi.org/10.1039/c3cc43833c	journal	January 2013
Energy-dispersive X-ray emission spectroscopy using an X-ray free-electron laser in a shot-by-shot mode Alonso-Mori, R.; Kern, J.; Gildea, R. J. Proceedings of the National Academy of Sciences, Vol. 109, Issue 47, p. 19103-19107 https://doi.org/10.1073/pnas.1211384109	journal	November 2012
Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated [ Co ( terpy ) 2 ] 2 + Biasin, Elisa; van Driel, Tim Brandt; Kjær, Kasper S. Physical Review Letters, Vol. 117, Issue 1 https://doi.org/10.1103/PhysRevLett.117.013002	journal	June 2016
Fe N -Heterocyclic Carbene Complexes as Promising Photosensitizers Liu, Yizhu; Persson, Petter; Sundström, Villy Accounts of Chemical Research, Vol. 49, Issue 8 https://doi.org/10.1021/acs.accounts.6b00186	journal	July 2016
Mixed Ligand Complexes of Iron(II) and (III) with Cyanide and Aromatic Di-imines Schilt, Alfred A. Journal of the American Chemical Society, Vol. 82, Issue 12 https://doi.org/10.1021/ja01497a007	journal	June 1960
Charge-Transfer Studies of Iron Cyano Compounds Bound to Nanocrystalline TiO ₂ Surfaces Yang, Mei; Thompson, David W.; Meyer, Gerald J. Inorganic Chemistry, Vol. 41, Issue 5 https://doi.org/10.1021/ic011069q	journal	March 2002
A low-spin Fe(iii) complex with 100-ps ligand-to-metal charge transfer photoluminescence Chábera, Pavel; Liu, Yizhu; Prakash, Om Nature, Vol. 543, Issue 7647 https://doi.org/10.1038/nature21430	journal	March 2017
Charge and Spin-State Characterization of Cobalt Bis( o -dioxolene) Valence Tautomers Using Co Kβ X-ray Emission and L-Edge X-ray Absorption Spectroscopies Liang, H. Winnie; Kroll, Thomas; Nordlund, Dennis Inorganic Chemistry, Vol. 56, Issue 2 https://doi.org/10.1021/acs.inorgchem.6b01666	journal	December 2016