Using Iron L-Edge and Nitrogen K-Edge X-ray Absorption Spectroscopy to Improve the Understanding of the Electronic Structure of Iron Carbene Complexes
(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.
(Less)
- author
- organization
-
- LU Profile Area: Light and Materials
- Chemical Physics
- MAX IV Laboratory
- LTH Profile Area: Photon Science and Technology
- LTH Profile Area: Nanoscience and Semiconductor Technology
- Synchrotron Radiation Research
- NanoLund: Centre for Nanoscience
- Centre for Analysis and Synthesis
- eSSENCE: The e-Science Collaboration
- Computational Chemistry
- LINXS - Institute of advanced Neutron and X-ray Science
- publishing date
- 2024-07-08
- 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}}, }