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 W. Hartsock, Marco E. Reinhard, Sergey Koroidov, Lin Li, Amy Cordones, Olga Gordivska, Om Prakash, Yizhu Liu, Mads Laursen, Elisa Biasin, Frederik Beyer Kjær Hansen, Peter VesterMorten Christensen, Kristoffer Haldrup, Zoltán Németh, Dorottya Sárosiné Szemes, Éva Bajnóczi, György Vankó, Tim B. van Driel, Roberto Alonso-Mori, James Glownia, Silke Nelson, Marcin Sikorski, Henrik Till Lemke, Dimosthenis Sokaras, Sophie E. Canton, Asmus Ougaard Dohn, Klaus Braagaard Møller, Martin Meedom 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
Volume132
Issue number1
Pages (from-to)372-380
Number of pages9
ISSN0044-8249
DOIs
Publication statusPublished - 2020

Keywords

  • Femtochemie
  • Moleküldynamik
  • Photochemie
  • Photophysik
  • Röntgenspektroskopie

Cite this

Tatsuno, H., Kjær, K. S., Kunnus, K., Harlang, T. C. B., Timm, C., Guo, M., ... Uhlig, J. (2020). Hot branching dynamics in a light‐harvesting iron carbene complex revealed by ultrafast x‐ray emission spectroscopy. Angewandte Chemie, 132(1), 372-380. https://doi.org/10.1002/ange.201908065
Tatsuno, Hideyuki ; Kjær, Kasper Skov ; Kunnus, Kristjan ; Harlang, Tobias C. B. ; Timm, Cornelia ; Guo, Meiyuan ; Chabera, Pavel ; Fredin, Lisa A. ; Hartsock, Robert W. ; Reinhard, Marco E. ; Koroidov, Sergey ; Li, Lin ; Cordones, Amy ; Gordivska, Olga ; Prakash, Om ; Liu, Yizhu ; Laursen, Mads ; Biasin, Elisa ; Hansen, Frederik Beyer Kjær ; Vester, Peter ; Christensen, Morten ; Haldrup, Kristoffer ; Németh, Zoltán ; Sárosiné Szemes, Dorottya ; Bajnóczi, Éva ; Vankó, György ; van Driel, Tim B. ; Alonso-Mori, Roberto ; Glownia, James ; Nelson, Silke ; Sikorski, Marcin ; Lemke, Henrik Till ; Sokaras, Dimosthenis ; Canton, Sophie E. ; Dohn, Asmus Ougaard ; Møller, Klaus Braagaard ; Nielsen, Martin Meedom ; 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. 2020 ; Vol. 132, No. 1. pp. 372-380.
@article{dd1dae59fedc469bb6fbb119a0188766,
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 = "Femtochemie, Molek{\"u}ldynamik, Photochemie, Photophysik, R{\"o}ntgenspektroskopie",
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 W.} and Reinhard, {Marco E.} and Sergey Koroidov and Lin Li and Amy Cordones and Olga Gordivska and Om Prakash and Yizhu Liu and Mads Laursen and Elisa Biasin and Hansen, {Frederik Beyer Kj{\ae}r} 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 James Glownia and Silke Nelson and Marcin Sikorski and Lemke, {Henrik Till} and Dimosthenis Sokaras and Canton, {Sophie E.} and Dohn, {Asmus Ougaard} and M{\o}ller, {Klaus Braagaard} and Nielsen, {Martin Meedom} 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/ange.201908065",
language = "English",
volume = "132",
pages = "372--380",
journal = "Angewandte Chemie",
issn = "0044-8249",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",
number = "1",

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Tatsuno, H, Kjær, KS, Kunnus, K, Harlang, TCB, Timm, C, Guo, M, Chabera, P, Fredin, LA, Hartsock, RW, Reinhard, ME, Koroidov, S, Li, L, Cordones, A, Gordivska, O, Prakash, O, Liu, Y, Laursen, M, Biasin, E, Hansen, FBK, Vester, P, Christensen, M, Haldrup, K, Németh, Z, Sárosiné Szemes, D, Bajnóczi, É, Vankó, G, van Driel, TB, Alonso-Mori, R, Glownia, J, 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, vol. 132, no. 1, pp. 372-380. https://doi.org/10.1002/ange.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 W.; Reinhard, Marco E.; Koroidov, Sergey; Li, Lin; Cordones, Amy; Gordivska, Olga; Prakash, Om; Liu, Yizhu; Laursen, Mads; Biasin, Elisa; Hansen, Frederik Beyer Kjær; Vester, Peter; Christensen, Morten; Haldrup, Kristoffer; Németh, Zoltán; Sárosiné Szemes, Dorottya; Bajnóczi, Éva; Vankó, György; van Driel, Tim B.; Alonso-Mori, Roberto; Glownia, James; Nelson, Silke; Sikorski, Marcin; Lemke, Henrik Till; Sokaras, Dimosthenis; Canton, Sophie E.; Dohn, Asmus Ougaard; Møller, Klaus Braagaard; Nielsen, Martin Meedom; Gaffney, Kelly J.; Wärnmark, Kenneth; Sundström, Villy; Persson, Petter; Uhlig, Jens.

In: Angewandte Chemie, Vol. 132, No. 1, 2020, p. 372-380.

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 W.

AU - Reinhard, Marco E.

AU - Koroidov, Sergey

AU - Li, Lin

AU - Cordones, Amy

AU - Gordivska, Olga

AU - Prakash, Om

AU - Liu, Yizhu

AU - Laursen, Mads

AU - Biasin, Elisa

AU - Hansen, Frederik Beyer Kjær

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

AU - Nelson, Silke

AU - Sikorski, Marcin

AU - Lemke, Henrik Till

AU - Sokaras, Dimosthenis

AU - Canton, Sophie E.

AU - Dohn, Asmus Ougaard

AU - Møller, Klaus Braagaard

AU - Nielsen, Martin Meedom

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 - Femtochemie

KW - Moleküldynamik

KW - Photochemie

KW - Photophysik

KW - Röntgenspektroskopie

U2 - 10.1002/ange.201908065

DO - 10.1002/ange.201908065

M3 - Journal article

VL - 132

SP - 372

EP - 380

JO - Angewandte Chemie

JF - Angewandte Chemie

SN - 0044-8249

IS - 1

ER -