Boosting Vis/NIR Charge-Transfer Absorptions of Iron(II) Complexes by N-Alkylation and N-Deprotonation in the Ligand Backbone
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Andreas KC Mengel
- Christian Bissinger
- Matthias Dorn
- Oliver Back
- Christoph Foerster
- Katja Heinze
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000403150100016&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1002/chem.201700959
- eISSN
- 1521-3765
- Externe Identifier
- Clarivate Analytics Document Solution ID: EX3RN
- PubMed Identifier: 28383155
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 33
- Zeitschrift
- CHEMISTRY-A EUROPEAN JOURNAL
- Schlüsselwörter
- charge transfer
- excited states
- iron complexes
- ligand substitution
- tridentate ligands
- Paginierung
- 7920 - 7931
- Datum der Veröffentlichung
- 2017
- Status
- Published
- Titel
- Boosting Vis/NIR Charge-Transfer Absorptions of Iron(II) Complexes by N-Alkylation and N-Deprotonation in the Ligand Backbone
- Sub types
- Article
- Ausgabe der Zeitschrift
- 23
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Abstract
- <jats:title>Abstract</jats:title><jats:p>Reversing the metal‐to‐ligand charge transfer (<jats:sup>3</jats:sup>MLCT)/metal‐centered (<jats:sup>3</jats:sup>MC) excited state order in iron(II) complexes is a challenging objective, yet would finally result in long‐sought luminescent transition‐metal complexes with an earth‐abundant central ion. One approach to achieve this goal is based on low‐energy charge‐transfer absorptions in combination with a strong ligand field. Coordinating electron‐rich and electron‐poor tridentate oligopyridine ligands with large bite angles at iron(II) enables both low‐energy MLCT absorption bands around 590 nm and a strong ligand field. Variations of the electron‐rich ligand by introducing longer alkyl substituents destabilizes the iron(II) complex towards ligand substitution reactions while hardly affecting the optical properties. On the other hand, N‐deprotonation of the ligand backbone is feasible and reversible, yielding deep‐green complexes with charge‐transfer bands extending into the near‐IR region. Time‐dependent density functional theory calculations assign these absorption bands to transitions with dipole‐allowed ligand‐to‐ligand charge transfer character. This unique geometric and electronic situation establishes a further regulating screw to increase the energy gap between potentially emitting charge‐transfer states and the non‐radiative ligand field states of iron(II) dyes.</jats:p>
- Autoren
- Andreas KC Mengel
- Christian Bissinger
- Matthias Dorn
- Oliver Back
- Christoph Förster
- Katja Heinze
- DOI
- 10.1002/chem.201700959
- eISSN
- 1521-3765
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 33
- Zeitschrift
- Chemistry – A European Journal
- Sprache
- en
- Online publication date
- 2017
- Paginierung
- 7920 - 7931
- Datum der Veröffentlichung
- 2017
- Status
- Published
- Herausgeber
- Wiley
- Herausgeber URL
- http://dx.doi.org/10.1002/chem.201700959
- Datum der Datenerfassung
- 2023
- Titel
- Boosting Vis/NIR Charge‐Transfer Absorptions of Iron(II) Complexes by N‐Alkylation and N‐Deprotonation in the Ligand Backbone
- Ausgabe der Zeitschrift
- 23
Datenquelle: Crossref
- Abstract
- Reversing the metal-to-ligand charge transfer (<sup>3</sup> MLCT)/metal-centered (<sup>3</sup> MC) excited state order in iron(II) complexes is a challenging objective, yet would finally result in long-sought luminescent transition-metal complexes with an earth-abundant central ion. One approach to achieve this goal is based on low-energy charge-transfer absorptions in combination with a strong ligand field. Coordinating electron-rich and electron-poor tridentate oligopyridine ligands with large bite angles at iron(II) enables both low-energy MLCT absorption bands around 590 nm and a strong ligand field. Variations of the electron-rich ligand by introducing longer alkyl substituents destabilizes the iron(II) complex towards ligand substitution reactions while hardly affecting the optical properties. On the other hand, N-deprotonation of the ligand backbone is feasible and reversible, yielding deep-green complexes with charge-transfer bands extending into the near-IR region. Time-dependent density functional theory calculations assign these absorption bands to transitions with dipole-allowed ligand-to-ligand charge transfer character. This unique geometric and electronic situation establishes a further regulating screw to increase the energy gap between potentially emitting charge-transfer states and the non-radiative ligand field states of iron(II) dyes.
- Addresses
- Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
- Autoren
- Andreas KC Mengel
- Christian Bissinger
- Matthias Dorn
- Oliver Back
- Christoph Förster
- Katja Heinze
- DOI
- 10.1002/chem.201700959
- eISSN
- 1521-3765
- Externe Identifier
- PubMed Identifier: 28383155
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft: GRK 1404
- Open access
- false
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 33
- Zeitschrift
- Chemistry (Weinheim an der Bergstrasse, Germany)
- Sprache
- eng
- Medium
- Print-Electronic
- Online publication date
- 2017
- Paginierung
- 7920 - 7931
- Datum der Veröffentlichung
- 2017
- Status
- Published
- Datum der Datenerfassung
- 2017
- Titel
- Boosting Vis/NIR Charge-Transfer Absorptions of Iron(II) Complexes by N-Alkylation and N-Deprotonation in the Ligand Backbone.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 23
Datenquelle: Europe PubMed Central
- Abstract
- Reversing the metal-to-ligand charge transfer (3 MLCT)/metal-centered (3 MC) excited state order in iron(II) complexes is a challenging objective, yet would finally result in long-sought luminescent transition-metal complexes with an earth-abundant central ion. One approach to achieve this goal is based on low-energy charge-transfer absorptions in combination with a strong ligand field. Coordinating electron-rich and electron-poor tridentate oligopyridine ligands with large bite angles at iron(II) enables both low-energy MLCT absorption bands around 590 nm and a strong ligand field. Variations of the electron-rich ligand by introducing longer alkyl substituents destabilizes the iron(II) complex towards ligand substitution reactions while hardly affecting the optical properties. On the other hand, N-deprotonation of the ligand backbone is feasible and reversible, yielding deep-green complexes with charge-transfer bands extending into the near-IR region. Time-dependent density functional theory calculations assign these absorption bands to transitions with dipole-allowed ligand-to-ligand charge transfer character. This unique geometric and electronic situation establishes a further regulating screw to increase the energy gap between potentially emitting charge-transfer states and the non-radiative ligand field states of iron(II) dyes.
- Autoren
- Andreas KC Mengel
- Christian Bissinger
- Matthias Dorn
- Oliver Back
- Christoph Förster
- Katja Heinze
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/28383155
- DOI
- 10.1002/chem.201700959
- eISSN
- 1521-3765
- Ausgabe der Veröffentlichung
- 33
- Zeitschrift
- Chemistry
- Schlüsselwörter
- charge transfer
- excited states
- iron complexes
- ligand substitution
- tridentate ligands
- Sprache
- eng
- Country
- Germany
- Paginierung
- 7920 - 7931
- Datum der Veröffentlichung
- 2017
- Status
- Published
- Datum, an dem der Datensatz öffentlich gemacht wurde
- 2018
- Titel
- Boosting Vis/NIR Charge-Transfer Absorptions of Iron(II) Complexes by N-Alkylation and N-Deprotonation in the Ligand Backbone.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 23
Datenquelle: PubMed
- Beziehungen:
-