- Understanding and controlling properties of transition metal complexes is a crucial step towards tailoring materials for sustainable energy applications. In a systematic approach, we use resonant inelastic X-ray scattering to study the influence of ligand substitution on the valence electronic structure around an aqueous iron(II) center. Exchanging cyanide with 2-2′-bipyridine ligands reshapes frontier orbitals in a way that reduces metal 3d charge delocalization onto the ligands. This net decrease of metal–ligand covalency results in lower metal-centered excited state energies in agreement with previously reported excited state dynamics. Furthermore, traces of solvent-effects were found indicating a varying interaction strength of the solvent with ligands of different character. Our results demonstrate how ligand exchange can be exploited to shape frontier orbitals of transition metal complexes in solution-phase chemistry; insights upon which future efforts can built when tailoring the functionality of photoactive systems forUnderstanding and controlling properties of transition metal complexes is a crucial step towards tailoring materials for sustainable energy applications. In a systematic approach, we use resonant inelastic X-ray scattering to study the influence of ligand substitution on the valence electronic structure around an aqueous iron(II) center. Exchanging cyanide with 2-2′-bipyridine ligands reshapes frontier orbitals in a way that reduces metal 3d charge delocalization onto the ligands. This net decrease of metal–ligand covalency results in lower metal-centered excited state energies in agreement with previously reported excited state dynamics. Furthermore, traces of solvent-effects were found indicating a varying interaction strength of the solvent with ligands of different character. Our results demonstrate how ligand exchange can be exploited to shape frontier orbitals of transition metal complexes in solution-phase chemistry; insights upon which future efforts can built when tailoring the functionality of photoactive systems for light-harvesting applications.…
MetadatenAuthor details: | Raphael Martin JayORCiDGND, Sebastian EckertORCiDGND, Mattis FondellORCiD, Piter S. MiedemaORCiD, Jesper NorellORCiD, Annette PietzschORCiD, Wilson Quevedo, Johannes Niskanen, Kristjan KunnusORCiD, Alexander FöhlischORCiDGND |
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DOI: | https://doi.org/10.1039/c8cp04341h |
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ISSN: | 1463-9076 |
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ISSN: | 1463-9084 |
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Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/30211412 |
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Title of parent work (English): | Physical chemistry, chemical physics : a journal of European Chemical Societies |
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Publisher: | Royal Society of Chemistry |
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Place of publishing: | Cambridge |
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Publication type: | Article |
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Language: | English |
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Date of first publication: | 2018/09/13 |
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Publication year: | 2018 |
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Release date: | 2021/06/29 |
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Volume: | 20 |
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Issue: | 44 |
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Number of pages: | 7 |
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First page: | 27745 |
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Last Page: | 27751 |
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Funding institution: | ERC-ADG-2014 - Advanced Investigator Grant under the Horizon 2020 EU Framework Program for Research and Innovation [669531 EDAX] |
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Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
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DDC classification: | 5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik |
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Peer review: | Referiert |
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Publishing method: | Open Access / Hybrid Open-Access |
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License (English): | Creative Commons - Namensnennung - Nicht-kommerziell - Keine Bearbeitung 3.0 Unported |
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