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http://doi.org/10.25358/openscience-8702
Autoren: | Moll, Johannes Naumann, Robert Sorge, Lukas Förster, Christoph Gessner, Niklas Burkhardt, Lukas Ugur, Naz Nuernberger, Patrick Seidel, Wolfram Ramanan, Charusheela Bauer, Matthias Heinze, Katja |
Titel: | Pseudo-octahedral iron(II) complexes with near-degenerate charge transfer and ligand field states at the Franck-Condon geometry |
Online-Publikationsdatum: | 30-Jan-2023 |
Erscheinungsdatum: | 2022 |
Sprache des Dokuments: | Englisch |
Zusammenfassung/Abstract: | Increasing the metal-to-ligand charge transfer (MLCT) excited state lifetime of polypyridine iron(II) complexes can be achieved by lowering the ligand's π* orbital energy and by increasing the ligand field splitting. In the homo- and heteroleptic complexes [Fe(cpmp)2]2+ (12+) and [Fe(cpmp)(ddpd)]2+ (22+) with the tridentate ligands 6,2’’-carboxypyridyl-2,2’-methylamine-pyridyl-pyridine (cpmp) and N,N’-dimethyl-N,N’-di-pyridin-2-ylpyridine-2,6-diamine (ddpd) two or one dipyridyl ketone moieties provide low energy π* acceptor orbitals. A good metal-ligand orbital overlap to increase the ligand field splitting is achieved by optimizing the octahedricity through CO and NMe units between the coordinating pyridines which enable the formation of six-membered chelate rings. The push-pull ligand cpmp provides intra-ligand and ligand-to-ligand charge transfer (ILCT, LL'CT) excited states in addition to MLCT excited states. Ground and excited state properties of 12+ and 22+ were accessed by X-ray diffraction analyses, resonance Raman spectroscopy, (spectro)electrochemistry, EPR spectroscopy, X-ray emission spectroscopy, static and time-resolved IR and UV/Vis/NIR absorption spectroscopy as well as quantum chemical calculations. |
DDC-Sachgruppe: | 540 Chemie 540 Chemistry and allied sciences |
Veröffentlichende Institution: | Johannes Gutenberg-Universität Mainz |
Organisationseinheit: | FB 09 Chemie, Pharmazie u. Geowissensch. |
Veröffentlichungsort: | Mainz |
ROR: | https://ror.org/023b0x485 |
DOI: | http://doi.org/10.25358/openscience-8702 |
Version: | Published version |
Publikationstyp: | Zeitschriftenaufsatz |
Nutzungsrechte: | CC BY-NC |
Informationen zu den Nutzungsrechten: | https://creativecommons.org/licenses/by-nc/4.0/ |
Zeitschrift: | Chemistry - a European journal 28 57 |
Seitenzahl oder Artikelnummer: | e202201858 |
Verlag: | Wiley-VCH |
Verlagsort: | Weinheim |
Erscheinungsdatum: | 2022 |
ISSN: | 1521-3765 |
DOI der Originalveröffentlichung: | 10.1002/chem.202201858 |
Enthalten in den Sammlungen: | DFG-491381577-H |
Dateien zu dieser Ressource:
Datei | Beschreibung | Größe | Format | ||
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![]() | pseudooctahedral_ironii_compl-20230127164246840.pdf | 2.56 MB | Adobe PDF | Öffnen/Anzeigen |