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Vibrational Coherence Spectroscopy Identifies Ultrafast Branching in an Iron(II) Sensitizer

Title: Vibrational Coherence Spectroscopy Identifies Ultrafast Branching in an Iron(II) Sensitizer
Authors: Hainer, F.; Alagna, N.; Reddy Marri, A.; Penfold, T.; Gros, Philippe; Haacke, S.; Buckup, T.
Contributors: Universität Heidelberg Heidelberg = Heidelberg University; Laboratoire Lorrain de Chimie Moléculaire (L2CM); Institut de Chimie - CNRS Chimie (INC-CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS); Newcastle University Newcastle; Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS); Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE); Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique; Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS); ANR-16-CE07-0013,PhotIron,Design de complexes de fer à propriétés photophysiques applicables(2016); ANR-10-IDEX-0002,UNISTRA,Par-delà les frontières, l'Université de Strasbourg(2010); ANR-20-SFRI-0012,STRAT'US,Façonner les talents en formation et en recherche à l'Université de Strasbourg(2020); ANR-17-EURE-0024,QMAT,Quantum Science and Nanomaterials(2017)
Source: ISSN: 1948-7185.
Publisher Information: CCSD; American Chemical Society
Publication Year: 2021
Collection: Université de Lorraine: HAL
Subject Terms: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Description: International audience ; The introduction of N-heterocyclic carbene ligands has greatly increased the lifetimes of metal-to-ligand charge transfer states (MLCT) in iron(II) complexes, making them promising candidates for photocatalytic applications. However, the spectrally elusive triplet metal-centered state (3MC) has been suggested to play a decisive role in the relaxation of the MLCT manifold to the ground state, shortening their lifetimes and consequently limiting the application potential. In this work, time-resolved vibrational spectroscopy and quantum chemical calculations are applied to shed light on the 3MCs’ involvement in the deactivation of the MLCT manifold of an iron(II) sensitizer. Two distinct symmetric Fe–L breathing vibrations at frequencies below 150 cm–1 are assigned to the 3MC and 3MLCT states by quantum chemical calculations. On the basis of this assignment, an ultrafast branching directly after excitation forms not only the long-lived 3MLCT but also the 3MC as an additional loss channel.
Document Type: article in journal/newspaper
Language: English
DOI: 10.1021/acs.jpclett.1c01580
Availability: https://hal.science/hal-03335923; https://hal.science/hal-03335923v1/document; https://hal.science/hal-03335923v1/file/Manuscript%20Fe-Complexes-reviewed_FINAL.pdf; https://doi.org/10.1021/acs.jpclett.1c01580
Rights: https://about.hal.science/hal-authorisation-v1/ ; info:eu-repo/semantics/OpenAccess
Accession Number: edsbas.E7296C
Database: BASE