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