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Using Iron L-Edge and Nitrogen K-Edge X-ray Absorption Spectroscopy to Improve the Understanding of the Electronic Structure of Iron Carbene Complexes

Guo, Meiyuan LU ; Temperton, Robert LU ; D’Acunto, Giulio ; Johansson, Niclas LU ; Jones, Rosemary LU ; Handrup, Karsten LU ; Ringelband, Sven LU ; Prakash, Om LU ; Fan, Hao LU and de Groot, Lisa H. M. LU , et al. (2024) In Inorganic Chemistry 63(27). p.12457-12468
Abstract

Iron-centered N-heterocyclic carbene compounds have attracted much attention in recent years due to their long-lived excited states with charge transfer (CT) character. Understanding the orbital interactions between the metal and ligand orbitals is of great importance for the rational tuning of the transition metal compound properties, e.g., for future photovoltaic and photocatalytic applications. Here, we investigate a series of iron-centered N-heterocyclic carbene complexes with +2, + 3, and +4 oxidation states of the central iron ion using iron L-edge and nitrogen K-edge X-ray absorption spectroscopy (XAS). The experimental Fe L-edge XAS data were simulated and interpreted through restricted-active space (RAS) and multiplet... (More)

Iron-centered N-heterocyclic carbene compounds have attracted much attention in recent years due to their long-lived excited states with charge transfer (CT) character. Understanding the orbital interactions between the metal and ligand orbitals is of great importance for the rational tuning of the transition metal compound properties, e.g., for future photovoltaic and photocatalytic applications. Here, we investigate a series of iron-centered N-heterocyclic carbene complexes with +2, + 3, and +4 oxidation states of the central iron ion using iron L-edge and nitrogen K-edge X-ray absorption spectroscopy (XAS). The experimental Fe L-edge XAS data were simulated and interpreted through restricted-active space (RAS) and multiplet calculations. The experimental N K-edge XAS is simulated and compared with time-dependent density functional theory (TDDFT) calculations. Through the combination of the complementary Fe L-edge and N K-edge XAS, direct probing of the complex interplay of the metal and ligand character orbitals was possible. The σ-donating and π-accepting capabilities of different ligands are compared, evaluated, and discussed. The results show how X-ray spectroscopy, together with advanced modeling, can be a powerful tool for understanding the complex interplay of metal and ligand.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
63
issue
27
pages
12 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:38934422
  • scopus:85197059022
ISSN
0020-1669
DOI
10.1021/acs.inorgchem.4c01026
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2024 The Authors. Published by American Chemical Society.
id
31fa7c65-5f3b-4172-b4ba-99d22889f74e
date added to LUP
2024-08-09 14:40:56
date last changed
2024-08-14 14:24:54
@article{31fa7c65-5f3b-4172-b4ba-99d22889f74e,
  abstract     = {{<p>Iron-centered N-heterocyclic carbene compounds have attracted much attention in recent years due to their long-lived excited states with charge transfer (CT) character. Understanding the orbital interactions between the metal and ligand orbitals is of great importance for the rational tuning of the transition metal compound properties, e.g., for future photovoltaic and photocatalytic applications. Here, we investigate a series of iron-centered N-heterocyclic carbene complexes with +2, + 3, and +4 oxidation states of the central iron ion using iron L-edge and nitrogen K-edge X-ray absorption spectroscopy (XAS). The experimental Fe L-edge XAS data were simulated and interpreted through restricted-active space (RAS) and multiplet calculations. The experimental N K-edge XAS is simulated and compared with time-dependent density functional theory (TDDFT) calculations. Through the combination of the complementary Fe L-edge and N K-edge XAS, direct probing of the complex interplay of the metal and ligand character orbitals was possible. The σ-donating and π-accepting capabilities of different ligands are compared, evaluated, and discussed. The results show how X-ray spectroscopy, together with advanced modeling, can be a powerful tool for understanding the complex interplay of metal and ligand.</p>}},
  author       = {{Guo, Meiyuan and Temperton, Robert and D’Acunto, Giulio and Johansson, Niclas and Jones, Rosemary and Handrup, Karsten and Ringelband, Sven and Prakash, Om and Fan, Hao and de Groot, Lisa H. M. and Hlynsson, Valtýr Freyr and Kaufhold, Simon and Gordivska, Olga and Velásquez González, Nicolás and Wärnmark, Kenneth and Schnadt, Joachim and Persson, Petter and Uhlig, Jens}},
  issn         = {{0020-1669}},
  language     = {{eng}},
  month        = {{07}},
  number       = {{27}},
  pages        = {{12457--12468}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Inorganic Chemistry}},
  title        = {{Using Iron L-Edge and Nitrogen K-Edge X-ray Absorption Spectroscopy to Improve the Understanding of the Electronic Structure of Iron Carbene Complexes}},
  url          = {{http://dx.doi.org/10.1021/acs.inorgchem.4c01026}},
  doi          = {{10.1021/acs.inorgchem.4c01026}},
  volume       = {{63}},
  year         = {{2024}},
}