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

Lookup NU author(s): Professor Thomas Penfold



This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society, 2021.

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The introduction of N-heterocyclic carbene ligands hasgreatly increased the lifetimes of metal-to-ligand charge transfer states(MLCT) in iron(II) complexes, making them promising candidatesfor photocatalytic applications. However, the spectrally elusive tripletmetal-centered state (3MC) has been suggested to play a decisive rolein the relaxation of the MLCT manifold to the ground state,shortening their lifetimes and consequently limiting the applicationpotential. In this work, time-resolved vibrational spectroscopy andquantum 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 atfrequencies below 150 cm−1 are assigned to the 3MC and 3MLCTstates by quantum chemical calculations. On the basis of thisassignment, an ultrafast branching directly after excitation forms not only the long-lived 3MLCT but also the 3MC as an additional loss channel.

Publication metadata

Author(s): Hainer F, Alagna N, Reddy A, Penfold TJ, Gros PC, Haacke S, Buckup T

Publication type: Article

Publication status: Published

Journal: Journal of Physical Chemistry Letters

Year: 2021

Volume: 12

Pages: 8560-8565

Print publication date: 01/09/2021

Online publication date: 01/09/2021

Acceptance date: 19/08/2021

Date deposited: 02/09/2021

ISSN (electronic): 1948-7185

Publisher: American Chemical Society


DOI: 10.1021/acs.jpclett.1c01580


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