Pseudo-Octahedral Iron(II) Complexes with Near-Degenerate Charge Transfer and Ligand Field States at the Franck-Condon Geometry

Publication type:
Journal article
Metadata:
Autoren
  • Johannes Moll
  • Robert Naumann
  • Lukas Sorge
  • Christoph Foerster
  • Niklas Gessner
  • Lukas Burkhardt
  • Naz Ugur
  • Patrick Nuernberger
  • Wolfram Seidel
  • Charusheela Ramanan
  • Matthias Bauer
  • Katja Heinze
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000839542500001&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1002/chem.202201858
eISSN
1521-3765
Externe Identifier
  • Clarivate Analytics Document Solution ID: 5H0EZ
  • PubMed Identifier: 35862259
ISSN
0947-6539
Ausgabe der Veröffentlichung
57
Zeitschrift
CHEMISTRY-A EUROPEAN JOURNAL
Schlüsselwörter
  • iron
  • photophysics
  • polypyridine ligands
  • time-resolved spectroscopy
  • tridentate ligands
Artikelnummer
ARTN e202201858
Datum der Veröffentlichung
2022
Status
Published
Titel
Pseudo-Octahedral Iron(II) Complexes with Near-Degenerate Charge Transfer and Ligand Field States at the Franck-Condon Geometry
Sub types
  • Article
Ausgabe der Zeitschrift
28

Data source: Web of Science (Lite)

Other metadata sources:
Abstract
<jats:title>Abstract</jats:title><jats:p>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)<jats:sub>2</jats:sub>]<jats:sup>2+</jats:sup>(<jats:bold>1<jats:sup>2+</jats:sup></jats:bold>) and [Fe(cpmp)(ddpd)]<jats:sup>2+</jats:sup>(<jats:bold>2<jats:sup>2+</jats:sup></jats:bold>) with the tridentate ligands 6,2’’‐carboxypyridyl‐2,2’‐methylamine‐pyridyl‐pyridine (cpmp) and<jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>’‐dimethyl‐<jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>’‐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<jats:bold>1<jats:sup>2+</jats:sup></jats:bold>and<jats:bold>2<jats:sup>2+</jats:sup></jats:bold>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.</jats:p>
Autoren
  • Johannes Moll
  • Robert Naumann
  • Lukas Sorge
  • Christoph Förster
  • Niklas Gessner
  • Lukas Burkhardt
  • Naz Ugur
  • Patrick Nuernberger
  • Wolfram Seidel
  • Charusheela Ramanan
  • Matthias Bauer
  • Katja Heinze
DOI
10.1002/chem.202201858
eISSN
1521-3765
ISSN
0947-6539
Ausgabe der Veröffentlichung
57
Zeitschrift
Chemistry – A European Journal
Sprache
en
Online publication date
2022
Datum der Veröffentlichung
2022
Status
Published
Herausgeber
Wiley
Herausgeber URL
http://dx.doi.org/10.1002/chem.202201858
Datum der Datenerfassung
2023
Titel
Pseudo‐Octahedral Iron(II) Complexes with Near‐Degenerate Charge Transfer and Ligand Field States at the Franck‐Condon Geometry
Ausgabe der Zeitschrift
28

Data source: Crossref

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)<sub>2</sub> ]<sup>2+</sup> (1<sup>2+</sup> ) and [Fe(cpmp)(ddpd)]<sup>2+</sup> (2<sup>2+</sup> ) 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 1<sup>2+</sup> and 2<sup>2+</sup> 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.
Addresses
  • Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Autoren
  • Johannes Moll
  • Robert Naumann
  • Lukas Sorge
  • Christoph Förster
  • Niklas Gessner
  • Lukas Burkhardt
  • Naz Ugur
  • Patrick Nuernberger
  • Wolfram Seidel
  • Charusheela Ramanan
  • Matthias Bauer
  • Katja Heinze
DOI
10.1002/chem.202201858
eISSN
1521-3765
Externe Identifier
  • PubMed Identifier: 35862259
  • PubMed Central ID: PMC9804653
Funding acknowledgements
  • Deutsche Forschungsgemeinschaft: HE 2778/14-1
  • Deutsche Forschungsgemeinschaft: NU 263/4-1
  • Deutsche Forschungsgemeinschaft: BA 4467/7-1
Open access
true
ISSN
0947-6539
Ausgabe der Veröffentlichung
57
Zeitschrift
Chemistry (Weinheim an der Bergstrasse, Germany)
Sprache
eng
Medium
Print-Electronic
Online publication date
2022
Open access status
Open Access
Paginierung
e202201858
Datum der Veröffentlichung
2022
Status
Published
Publisher licence
CC BY-NC
Datum der Datenerfassung
2022
Titel
Pseudo-Octahedral Iron(II) Complexes with Near-Degenerate Charge Transfer and Ligand Field States at the Franck-Condon Geometry.
Sub types
  • research-article
  • Journal Article
Ausgabe der Zeitschrift
28

Files

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/chem.202201858 https://europepmc.org/articles/PMC9804653?pdf=render

Data source: Europe PubMed Central

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.
Autoren
  • Johannes Moll
  • Robert Naumann
  • Lukas Sorge
  • Christoph Förster
  • Niklas Gessner
  • Lukas Burkhardt
  • Naz Ugur
  • Patrick Nuernberger
  • Wolfram Seidel
  • Charusheela Ramanan
  • Matthias Bauer
  • Katja Heinze
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/35862259
DOI
10.1002/chem.202201858
eISSN
1521-3765
Externe Identifier
  • PubMed Central ID: PMC9804653
Funding acknowledgements
  • Deutsche Forschungsgemeinschaft: HE 2778/14-1
  • Deutsche Forschungsgemeinschaft: NU 263/4-1
  • Deutsche Forschungsgemeinschaft: BA 4467/7-1
Ausgabe der Veröffentlichung
57
Zeitschrift
Chemistry
Schlüsselwörter
  • iron
  • photophysics
  • polypyridine ligands
  • time-resolved spectroscopy
  • tridentate ligands
Sprache
eng
Country
Germany
Paginierung
e202201858
Datum der Veröffentlichung
2022
Status
Published
Titel
Pseudo-Octahedral Iron(II) Complexes with Near-Degenerate Charge Transfer and Ligand Field States at the Franck-Condon Geometry.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
28

Data source: PubMed

Author's licence
CC-BY-NC
Autoren
  • Johannes Moll
  • Robert Naumann
  • Lukas Sorge
  • Christoph Förster
  • Niklas Gessner
  • Lukas Burkhardt
  • Naz Ugur
  • Patrick Nuernberger
  • Wolfram Seidel
  • Charusheela Ramanan
  • Matthias Bauer
  • Katja Heinze
Hosting institution
Universitätsbibliothek Mainz
Sammlungen
  • DFG-491381577-H
Resource version
Published version
DOI
10.1002/chem.202201858
Funding acknowledgements
  • Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 491381577
File(s) embargoed
false
Open access
true
ISSN
1521-3765
Ausgabe der Veröffentlichung
57
Zeitschrift
Chemistry - a European journal
Schlüsselwörter
  • 540 Chemie
  • 540 Chemistry and allied sciences
Sprache
eng
Open access status
Open Access
Paginierung
e202201858
Datum der Veröffentlichung
2022
Public URL
https://openscience.ub.uni-mainz.de/handle/20.500.12030/8718
Herausgeber
Wiley-VCH
Datum der Datenerfassung
2023
Datum, an dem der Datensatz öffentlich gemacht wurde
2023
Zugang
Public
Titel
Pseudo-octahedral iron(II) complexes with near-degenerate charge transfer and ligand field states at the Franck-Condon geometry
Ausgabe der Zeitschrift
28

Files

pseudooctahedral_ironii_compl-20230127164246840.pdf

Data source: OPENSCIENCE.UB

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