Hot branching dynamics in a light-harvesting iron carbene complex revealed by ultrafast x-ray emission spectroscopy

Hideyuki Tatsuno, Kasper Skov Kjær, Kristjan Kunnus, Tobias C. B. Harlang, Cornelia Timm, Meiyuan Guo, Pavel Chabera, Lisa A. Fredin, Robert J. 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 VesterMorten Christensen, Kristoffer Haldrup, Zoltán Németh, Dorottya Sárosiné Szemes, Éva Bajnóczi, György Vankó, Tim van Driel, Roberto Alonso-Mori, James M. Glownia, Silke Nelson, Marcin Sikorski, Henrik Till 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*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Iron nitrogen heterocyclic carbenes (NHC) have received a great deal of attention recently, due to their growing potential as e.g light sensitizers and photocatalysts. We present a sub-ps x-ray spectroscopy study of a FeIINHC complex allowing us to identify and quantify the states involved in the deactivation cascade after light absorption. We find that excited molecules relax back to the ground state populating first the 3MLCT and then along two pathways the 3MC state. One of these pathways is ultrafast (~150 fs) for ~30% of the excited molecules, in competition with vibrational relaxation and cooling, followed by a much slower (7.6 ps) decay of the relaxed 3MLCT state. The 3MC state then rapidly (2.2 ps) decays to the ground state. The ultrafast deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen other FeNHC complexes (and perhaps other transition metal complexes) for this ultrafast decay of 3MLCT population, in order to optimize photochemical performance.
Original languageEnglish
JournalAngewandte Chemie International Edition
Volume59
Issue number1
Pages (from-to)364-372
Number of pages9
ISSN1433-7851
DOIs
Publication statusPublished - 2020

Keywords

  • Femtochemistry
  • Molecular dynamics
  • Photochemistry
  • Photophysics
  • X-ray spectroscopy

Cite this

Tatsuno, Hideyuki ; Kjær, Kasper Skov ; Kunnus, Kristjan ; Harlang, Tobias C. B. ; Timm, Cornelia ; Guo, Meiyuan ; Chabera, Pavel ; Fredin, Lisa A. ; Hartsock, Robert J. ; Reinhard, Marco E. ; Koroidov, Sergey ; Li, Lin ; Cordones, Amy A. ; Gordivska, Olga ; Prakash, Om ; Liu, Yizhu ; Laursen, Mads G. ; Biasin, Elisa ; Hansen, Frederik B. ; Vester, Peter ; Christensen, Morten ; Haldrup, Kristoffer ; Németh, Zoltán ; Sárosiné Szemes, Dorottya ; Bajnóczi, Éva ; Vankó, György ; van Driel, Tim ; Alonso-Mori, Roberto ; Glownia, James M. ; Nelson, Silke ; Sikorski, Marcin ; Lemke, Henrik Till ; Sokaras, Dimosthenis ; Canton, Sophie E. ; Dohn, Asmus O. ; Møller, Klaus B. ; Nielsen, Martin M. ; Gaffney, Kelly J. ; Wärnmark, Kenneth ; Sundström, Villy ; Persson, Petter ; Uhlig, Jens. / Hot branching dynamics in a light-harvesting iron carbene complex revealed by ultrafast x-ray emission spectroscopy. In: Angewandte Chemie International Edition. 2020 ; Vol. 59, No. 1. pp. 364-372.
@article{d649befe35db4746a18c8bf9b82b34e8,
title = "Hot branching dynamics in a light-harvesting iron carbene complex revealed by ultrafast x-ray emission spectroscopy",
abstract = "Iron nitrogen heterocyclic carbenes (NHC) have received a great deal of attention recently, due to their growing potential as e.g light sensitizers and photocatalysts. We present a sub-ps x-ray spectroscopy study of a FeIINHC complex allowing us to identify and quantify the states involved in the deactivation cascade after light absorption. We find that excited molecules relax back to the ground state populating first the 3MLCT and then along two pathways the 3MC state. One of these pathways is ultrafast (~150 fs) for ~30{\%} of the excited molecules, in competition with vibrational relaxation and cooling, followed by a much slower (7.6 ps) decay of the relaxed 3MLCT state. The 3MC state then rapidly (2.2 ps) decays to the ground state. The ultrafast deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen other FeNHC complexes (and perhaps other transition metal complexes) for this ultrafast decay of 3MLCT population, in order to optimize photochemical performance.",
keywords = "Femtochemistry, Molecular dynamics, Photochemistry, Photophysics, X-ray spectroscopy",
author = "Hideyuki Tatsuno and Kj{\ae}r, {Kasper Skov} and Kristjan Kunnus and Harlang, {Tobias C. B.} and Cornelia Timm and Meiyuan Guo and Pavel Chabera and Fredin, {Lisa A.} and Hartsock, {Robert J.} 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 and Roberto Alonso-Mori and Glownia, {James M.} and Silke Nelson and Marcin Sikorski and Lemke, {Henrik Till} 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",
year = "2020",
doi = "10.1002/anie.201908065",
language = "English",
volume = "59",
pages = "364--372",
journal = "Angewandte Chemie International Edition",
issn = "1433-7851",
publisher = "Wiley-VCH",
number = "1",

}

Tatsuno, H, Kjær, KS, Kunnus, K, Harlang, TCB, Timm, C, Guo, M, Chabera, P, Fredin, LA, Hartsock, RJ, 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, T, 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

Hot branching dynamics in a light-harvesting iron carbene complex revealed by ultrafast x-ray emission spectroscopy. / Tatsuno, Hideyuki; Kjær, Kasper Skov; Kunnus, Kristjan; Harlang, Tobias C. B.; Timm, Cornelia; Guo, Meiyuan; Chabera, Pavel; Fredin, Lisa A.; Hartsock, Robert J.; Reinhard, Marco E.; Koroidov, Sergey; Li, Lin; Cordones, Amy A.; Gordivska, Olga; Prakash, Om; Liu, Yizhu; Laursen, Mads G.; Biasin, Elisa; Hansen, Frederik B.; Vester, Peter; Christensen, Morten; Haldrup, Kristoffer; Németh, Zoltán; Sárosiné Szemes, Dorottya; Bajnóczi, Éva; Vankó, György; van Driel, Tim; Alonso-Mori, Roberto; Glownia, James M.; Nelson, Silke; Sikorski, Marcin; Lemke, Henrik Till; Sokaras, Dimosthenis; Canton, Sophie E.; Dohn, Asmus O.; Møller, Klaus B.; Nielsen, Martin M.; Gaffney, Kelly J.; Wärnmark, Kenneth; Sundström, Villy; Persson, Petter; Uhlig, Jens.

In: Angewandte Chemie International Edition, Vol. 59, No. 1, 2020, p. 364-372.

Research output: Contribution to journalJournal articleResearchpeer-review

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 Skov

AU - Kunnus, Kristjan

AU - Harlang, Tobias C. B.

AU - Timm, Cornelia

AU - Guo, Meiyuan

AU - Chabera, Pavel

AU - Fredin, Lisa A.

AU - Hartsock, Robert J.

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

AU - Alonso-Mori, Roberto

AU - Glownia, James M.

AU - Nelson, Silke

AU - Sikorski, Marcin

AU - Lemke, Henrik Till

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

PY - 2020

Y1 - 2020

N2 - Iron nitrogen heterocyclic carbenes (NHC) have received a great deal of attention recently, due to their growing potential as e.g light sensitizers and photocatalysts. We present a sub-ps x-ray spectroscopy study of a FeIINHC complex allowing us to identify and quantify the states involved in the deactivation cascade after light absorption. We find that excited molecules relax back to the ground state populating first the 3MLCT and then along two pathways the 3MC state. One of these pathways is ultrafast (~150 fs) for ~30% of the excited molecules, in competition with vibrational relaxation and cooling, followed by a much slower (7.6 ps) decay of the relaxed 3MLCT state. The 3MC state then rapidly (2.2 ps) decays to the ground state. The ultrafast deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen other FeNHC complexes (and perhaps other transition metal complexes) for this ultrafast decay of 3MLCT population, in order to optimize photochemical performance.

AB - Iron nitrogen heterocyclic carbenes (NHC) have received a great deal of attention recently, due to their growing potential as e.g light sensitizers and photocatalysts. We present a sub-ps x-ray spectroscopy study of a FeIINHC complex allowing us to identify and quantify the states involved in the deactivation cascade after light absorption. We find that excited molecules relax back to the ground state populating first the 3MLCT and then along two pathways the 3MC state. One of these pathways is ultrafast (~150 fs) for ~30% of the excited molecules, in competition with vibrational relaxation and cooling, followed by a much slower (7.6 ps) decay of the relaxed 3MLCT state. The 3MC state then rapidly (2.2 ps) decays to the ground state. The ultrafast deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen other FeNHC complexes (and perhaps other transition metal complexes) for this ultrafast decay of 3MLCT population, in order to optimize photochemical performance.

KW - Femtochemistry

KW - Molecular dynamics

KW - Photochemistry

KW - Photophysics

KW - X-ray spectroscopy

U2 - 10.1002/anie.201908065

DO - 10.1002/anie.201908065

M3 - Journal article

C2 - 31602726

VL - 59

SP - 364

EP - 372

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1433-7851

IS - 1

ER -