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

Tatsuno, Hideyuki; Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C.  B.; Timm, Cornelia; Guo, Meiyuan; Chàbera, Pavel; Fredin, Lisa A.; Hartsock, Robert W.; 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 B.; Alonso‐Mori, Roberto; Glownia, James M.; Nelson, Silke; Sikorski, Marcin; Lemke, Henrik T.; 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

doi:10.1002/anie.201908065

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

Journal Article · 10 October 2019 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201908065 · OSTI ID:1633958

Tatsuno, Hideyuki ^[1]; Kjær, Kasper S. ^[1];

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^[1]; Timm, Cornelia ^[1];

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^[1]; Hartsock, Robert W. ^[2];

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^[2]; Li, Lin ^[2];

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^[4]; Hansen, Frederik B. ^[3];

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Lund Univ. (Sweden)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Technical Univ. of Denmark, Lyngby (Denmark)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Technical Univ. of Denmark, Lyngby (Denmark)
Hungarian Academy of Sciences, Budapest (Hungary)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); ELI-HU Non-Profit Ltd., Szeged (Hungary)
Technical Univ. of Denmark, Lyngby (Denmark); Univ. of Iceland, Reykjavik (Iceland)

Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. Here, we present a sub-ps X-ray spectroscopy study of an Fe^IINHC complex that identifies 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 comand quantifies the states involved in the deactivation cascade after light petition 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.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Independent Research Fund Denmark; Icelandic Research Fund; European Union (EU); European Regional Development Fund; Hungarian Academy of Sciences; Government of Hungary; National Research, Development and Innovation Fund; Knut and Alice Wallenberg Foundation

Grant/Contract Number:: AC02-76SF00515; DFF‐4002‐00272; DFF‐8021‐00347B; 196279‐051; GINOP‐2.3.6‐15‐2015‐00001; LP2013‐59; VEKOP‐2.3.2–16–2017‐00015; NKFIH-FK-124460; KAW2014.0370

OSTI ID:: 1633958

Alternate ID(s):: OSTI ID: 1572578

Journal Information:: Angewandte Chemie (International Edition), Vol. 59, Issue 1; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 34 works

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