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Authors: Moll, Johannes
Naumann, Robert
Sorge, Lukas
Förster, Christoph
Gessner, Niklas
Burkhardt, Lukas
Ugur, Naz
Nuernberger, Patrick
Seidel, Wolfram
Ramanan, Charusheela
Bauer, Matthias
Heinze, Katja
Title: Pseudo-octahedral iron(II) complexes with near-degenerate charge transfer and ligand field states at the Franck-Condon geometry
Online publication date: 30-Jan-2023
Year of first publication: 2022
Language: english
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: 540 Chemie
540 Chemistry and allied sciences
Institution: Johannes Gutenberg-Universität Mainz
Department: FB 09 Chemie, Pharmazie u. Geowissensch.
Place: Mainz
Version: Published version
Publication type: Zeitschriftenaufsatz
License: CC BY-NC
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Journal: Chemistry - a European journal
Pages or article number: e202201858
Publisher: Wiley-VCH
Publisher place: Weinheim
Issue date: 2022
ISSN: 1521-3765
Publisher DOI: 10.1002/chem.202201858
Appears in collections:DFG-491381577-H

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