Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy

Hideyuki Tatsuno; Kasper S. Kjær; Kristjan Kunnus; Tobias C.B. Harlang; Cornelia Timm; Meiyuan Guo; Pavel Chàbera; Lisa A. Fredin; Robert W. Hartsock; Marco E. Reinhard; Sergey Koroidov; Lin Li; Amy A. Cordones; Olga Gordivska; Om Prakash; Yizhu Liu; Mads G. Laursen; Elisa Biasin; Frederik B. Hansen; Peter Vester; Morten Christensen; Kristoffer Haldrup; Zoltán Németh; Dorottya Sárosiné Szemes; Éva Bajnóczi; György Vankó; Tim B. Van Driel; Roberto Alonso-Mori; James M. Glownia; Silke Nelson; Marcin Sikorski; Henrik T. Lemke; Dimosthenis Sokaras; Sophie E. Canton; Asmus O. Dohn; Klaus B. Møller; Martin M. Nielsen; Kelly J. Gaffney; Kenneth Wärnmark; Villy Sundström; Petter Persson; Jens Uhlig

doi:10.1002/anie.201908065

Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy

Hideyuki Tatsuno
, Kasper S. Kjær
, Kristjan Kunnus
, Tobias C.B. Harlang
, Cornelia Timm
, Meiyuan Guo
, Pavel Chàbera
, Lisa A. Fredin
, Robert W. Hartsock
, Marco E. Reinhard
, Sergey Koroidov
, Lin Li
, Amy A. Cordones
, Olga Gordivska
, Om Prakash
, Yizhu Liu
, Mads G. Laursen
, Elisa Biasin
, Frederik B. Hansen
, Peter Vester

Morten Christensen, Kristoffer Haldrup, Zoltán Németh, Dorottya Sárosiné Szemes, Éva Bajnóczi, György Vankó, Tim B. Van Driel, Roberto Alonso-Mori, James M. Glownia, Silke Nelson, Marcin Sikorski, Henrik T. Lemke, Dimosthenis Sokaras, Sophie E. Canton, Asmus O. Dohn, Klaus B. Møller, Martin M. Nielsen, Kelly J. Gaffney, Kenneth Wärnmark, Villy Sundström, Petter Persson, Jens Uhlig

Science Institute

University of Iceland

Research output: Contribution to journal › Article › peer-review

Abstract

Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an Fe^IINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot ³MLCT state, from the initially excited ¹MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the ³MC state, in competition with vibrational relaxation and cooling to the relaxed ³MLCT state. The relaxed ³MLCT state then decays much more slowly (7.6 ps) to the ³MC state. The ³MC state is rapidly (2.2 ps) deactivated to the ground state. The ⁵MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the ³MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.

Original language	English
Pages (from-to)	364-372
Number of pages	9
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	1
DOIs	https://doi.org/10.1002/anie.201908065
Publication status	Published - 2 Jan 2020

Bibliographical note

Funding Information: P.P. acknowledges support from the Crafoord Foundation, the Knut and Alice Wallenberg Foundation (KAW), the Swedish Research Council (VR), the Swedish Energy Agency (Energimyndigheten), and the Swedish Foundation for Strategic Research (SSF). J.U. acknowledges support from the Crafoord Foundation, the Knut and Alice Wallenberg Foundation (KAW), and from the Trygger Foundation. The DTU-affiliated authors gratefully acknowledge DANSCATT for supporting the beamtime efforts. M.M.N., M.G.L., E.B., A.O.D., and K.B.M. thank the Independent Research Fund Denmark for financial support under Grants No. DFF-4002-00272 and No. DFF-8021-00347B. A.O.D. acknowledges support from the Icelandic Research Fund, Grant 196279-051. S.E.C. acknowledges funding from the Helmholtz Recognition Award. The ELI-ALPS project (GINOP-2.3.6-15-2015-00001) is financed by the European Union and co-financed by the European Regional Development Fund. This work is in part financed by the ?Lend?let? (Momentum) Program of the Hungarian Academy of Sciences (LP2013-59), the Government of Hungary and the European Regional Development Fund under Grant VEKOP-2.3.2?16?2017-00015, and the National Research, Development and Innovation Fund (NKFIH FK 124460). Work by K.K., M.E.R., A.A.C., and K.J.G. was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. S.K. and L.L. thank The Knut and Alice Wallenberg Foundation (KAW2014.0370) for financial support. Use of the Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE?AC02?76SF00515. Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Other keywords

X-ray spectroscopy
femtochemistry
molecular dynamics
photochemistry
photophysics

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Cite this

Tatsuno, H., Kjær, K. S., Kunnus, K., Harlang, T. C. B., Timm, C., Guo, M., Chàbera, P., Fredin, L. A., Hartsock, R. W., Reinhard, M. E., Koroidov, S., Li, L., Cordones, A. A., Gordivska, O., Prakash, O., Liu, Y., Laursen, M. G., Biasin, E., Hansen, F. B., ... Uhlig, J. (2020). Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy. Angewandte Chemie - International Edition, 59(1), 364-372. https://doi.org/10.1002/anie.201908065

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title = "Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy",

abstract = "Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an FeIINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3MLCT state, from the initially excited 1MLCT state, 30 \% of the molecules undergo ultrafast (150 fs) relaxation to the 3MC state, in competition with vibrational relaxation and cooling to the relaxed 3MLCT state. The relaxed 3MLCT state then decays much more slowly (7.6 ps) to the 3MC state. The 3MC state is rapidly (2.2 ps) deactivated to the ground state. The 5MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.",

keywords = "X-ray spectroscopy, femtochemistry, molecular dynamics, photochemistry, photophysics",

author = "Hideyuki Tatsuno and Kj{\ae}r, \{Kasper S.\} and Kristjan Kunnus and Harlang, \{Tobias C.B.\} and Cornelia Timm and Meiyuan Guo and Pavel Ch{\`a}bera and Fredin, \{Lisa A.\} and Hartsock, \{Robert W.\} and Reinhard, \{Marco E.\} and Sergey Koroidov and Lin Li and Cordones, \{Amy A.\} and Olga Gordivska and Om Prakash and Yizhu Liu and Laursen, \{Mads G.\} and Elisa Biasin and Hansen, \{Frederik B.\} and Peter Vester and Morten Christensen and Kristoffer Haldrup and Zolt{\'a}n N{\'e}meth and \{S{\'a}rosin{\'e} Szemes\}, Dorottya and {\'E}va Bajn{\'o}czi and Gy{\"o}rgy Vank{\'o} and \{Van Driel\}, \{Tim B.\} and Roberto Alonso-Mori and Glownia, \{James M.\} and Silke Nelson and Marcin Sikorski and Lemke, \{Henrik T.\} and Dimosthenis Sokaras and Canton, \{Sophie E.\} and Dohn, \{Asmus O.\} and M{\o}ller, \{Klaus B.\} and Nielsen, \{Martin M.\} and Gaffney, \{Kelly J.\} and Kenneth W{\"a}rnmark and Villy Sundstr{\"o}m and Petter Persson and Jens Uhlig",

note = "Funding Information: P.P. acknowledges support from the Crafoord Foundation, the Knut and Alice Wallenberg Foundation (KAW), the Swedish Research Council (VR), the Swedish Energy Agency (Energimyndigheten), and the Swedish Foundation for Strategic Research (SSF). J.U. acknowledges support from the Crafoord Foundation, the Knut and Alice Wallenberg Foundation (KAW), and from the Trygger Foundation. The DTU-affiliated authors gratefully acknowledge DANSCATT for supporting the beamtime efforts. M.M.N., M.G.L., E.B., A.O.D., and K.B.M. thank the Independent Research Fund Denmark for financial support under Grants No. DFF-4002-00272 and No. DFF-8021-00347B. A.O.D. acknowledges support from the Icelandic Research Fund, Grant 196279-051. S.E.C. acknowledges funding from the Helmholtz Recognition Award. The ELI-ALPS project (GINOP-2.3.6-15-2015-00001) is financed by the European Union and co-financed by the European Regional Development Fund. This work is in part financed by the ?Lend?let? (Momentum) Program of the Hungarian Academy of Sciences (LP2013-59), the Government of Hungary and the European Regional Development Fund under Grant VEKOP-2.3.2?16?2017-00015, and the National Research, Development and Innovation Fund (NKFIH FK 124460). Work by K.K., M.E.R., A.A.C., and K.J.G. was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. S.K. and L.L. thank The Knut and Alice Wallenberg Foundation (KAW2014.0370) for financial support. Use of the Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE?AC02?76SF00515. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2020",

month = jan,

day = "2",

doi = "10.1002/anie.201908065",

language = "English",

volume = "59",

pages = "364--372",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "1",

}

Tatsuno, H, Kjær, KS, Kunnus, K, Harlang, TCB, Timm, C, Guo, M, Chàbera, P, Fredin, LA, Hartsock, RW, Reinhard, ME, Koroidov, S, Li, L, Cordones, AA, Gordivska, O, Prakash, O, Liu, Y, Laursen, MG, Biasin, E, Hansen, FB, Vester, P, Christensen, M, Haldrup, K, Németh, Z, Sárosiné Szemes, D, Bajnóczi, É, Vankó, G, Van Driel, TB, Alonso-Mori, R, Glownia, JM, Nelson, S, Sikorski, M, Lemke, HT, Sokaras, D, Canton, SE, Dohn, AO, Møller, KB, Nielsen, MM, Gaffney, KJ, Wärnmark, K, Sundström, V, Persson, P & Uhlig, J 2020, 'Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy', Angewandte Chemie - International Edition, vol. 59, no. 1, pp. 364-372. https://doi.org/10.1002/anie.201908065

TY - JOUR

T1 - Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy

AU - Tatsuno, Hideyuki

AU - Kjær, Kasper S.

AU - Kunnus, Kristjan

AU - Harlang, Tobias C.B.

AU - Timm, Cornelia

AU - Guo, Meiyuan

AU - Chàbera, Pavel

AU - Fredin, Lisa A.

AU - Hartsock, Robert W.

AU - Reinhard, Marco E.

AU - Koroidov, Sergey

AU - Li, Lin

AU - Cordones, Amy A.

AU - Gordivska, Olga

AU - Prakash, Om

AU - Liu, Yizhu

AU - Laursen, Mads G.

AU - Biasin, Elisa

AU - Hansen, Frederik B.

AU - Vester, Peter

AU - Christensen, Morten

AU - Haldrup, Kristoffer

AU - Németh, Zoltán

AU - Sárosiné Szemes, Dorottya

AU - Bajnóczi, Éva

AU - Vankó, György

AU - Van Driel, Tim B.

AU - Alonso-Mori, Roberto

AU - Glownia, James M.

AU - Nelson, Silke

AU - Sikorski, Marcin

AU - Lemke, Henrik T.

AU - Sokaras, Dimosthenis

AU - Canton, Sophie E.

AU - Dohn, Asmus O.

AU - Møller, Klaus B.

AU - Nielsen, Martin M.

AU - Gaffney, Kelly J.

AU - Wärnmark, Kenneth

AU - Sundström, Villy

AU - Persson, Petter

AU - Uhlig, Jens

N1 - Funding Information: P.P. acknowledges support from the Crafoord Foundation, the Knut and Alice Wallenberg Foundation (KAW), the Swedish Research Council (VR), the Swedish Energy Agency (Energimyndigheten), and the Swedish Foundation for Strategic Research (SSF). J.U. acknowledges support from the Crafoord Foundation, the Knut and Alice Wallenberg Foundation (KAW), and from the Trygger Foundation. The DTU-affiliated authors gratefully acknowledge DANSCATT for supporting the beamtime efforts. M.M.N., M.G.L., E.B., A.O.D., and K.B.M. thank the Independent Research Fund Denmark for financial support under Grants No. DFF-4002-00272 and No. DFF-8021-00347B. A.O.D. acknowledges support from the Icelandic Research Fund, Grant 196279-051. S.E.C. acknowledges funding from the Helmholtz Recognition Award. The ELI-ALPS project (GINOP-2.3.6-15-2015-00001) is financed by the European Union and co-financed by the European Regional Development Fund. This work is in part financed by the ?Lend?let? (Momentum) Program of the Hungarian Academy of Sciences (LP2013-59), the Government of Hungary and the European Regional Development Fund under Grant VEKOP-2.3.2?16?2017-00015, and the National Research, Development and Innovation Fund (NKFIH FK 124460). Work by K.K., M.E.R., A.A.C., and K.J.G. was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. S.K. and L.L. thank The Knut and Alice Wallenberg Foundation (KAW2014.0370) for financial support. Use of the Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE?AC02?76SF00515. Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/1/2

Y1 - 2020/1/2

N2 - Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an FeIINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3MLCT state, from the initially excited 1MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3MC state, in competition with vibrational relaxation and cooling to the relaxed 3MLCT state. The relaxed 3MLCT state then decays much more slowly (7.6 ps) to the 3MC state. The 3MC state is rapidly (2.2 ps) deactivated to the ground state. The 5MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.

AB - Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an FeIINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3MLCT state, from the initially excited 1MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3MC state, in competition with vibrational relaxation and cooling to the relaxed 3MLCT state. The relaxed 3MLCT state then decays much more slowly (7.6 ps) to the 3MC state. The 3MC state is rapidly (2.2 ps) deactivated to the ground state. The 5MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.

KW - X-ray spectroscopy

KW - femtochemistry

KW - molecular dynamics

KW - photochemistry

KW - photophysics

UR - https://www.scopus.com/pages/publications/85074827405

U2 - 10.1002/anie.201908065

DO - 10.1002/anie.201908065

M3 - Article

C2 - 31602726

SN - 1433-7851

VL - 59

SP - 364

EP - 372

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 1

ER -

Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy

Abstract

Bibliographical note

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