Bulky ligands protect molecular ruby from oxygen quenching

Publication type:
Journal article
Metadata:
Autoren
  • Laura Stein
  • Cui Wang
  • Christoph Foerster
  • Ute Resch-Genger
  • Katja Heinze
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000880788700001&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1039/d2dt02950b
eISSN
1477-9234
Externe Identifier
  • Clarivate Analytics Document Solution ID: 6P2MN
  • PubMed Identifier: 36342442
ISSN
1477-9226
Ausgabe der Veröffentlichung
46
Zeitschrift
DALTON TRANSACTIONS
Paginierung
17664 - 17670
Datum der Veröffentlichung
2022
Status
Published
Titel
Bulky ligands protect molecular ruby from oxygen quenching
Sub types
  • Article
Ausgabe der Zeitschrift
51

Data source: Web of Science (Lite)

Other metadata sources:
Abstract
<jats:p>Steric protection strongly reduces phosphorescence quenching of excited molecular rubies by oxygen. The most bulky ligand enables photoluminescence quantum yields up to 5.1% and lifetimes up to 518 µs in air-saturated acetonitrile.</jats:p>
Autoren
  • Laura Stein
  • Cui Wang
  • Christoph Förster
  • Ute Resch-Genger
  • Katja Heinze
DOI
10.1039/d2dt02950b
eISSN
1477-9234
ISSN
1477-9226
Ausgabe der Veröffentlichung
46
Zeitschrift
Dalton Transactions
Sprache
en
Online publication date
2022
Paginierung
17664 - 17670
Status
Published online
Herausgeber
Royal Society of Chemistry (RSC)
Herausgeber URL
http://dx.doi.org/10.1039/d2dt02950b
Datum der Datenerfassung
2024
Titel
Bulky ligands protect molecular ruby from oxygen quenching
Ausgabe der Zeitschrift
51

Data source: Crossref

Abstract
Chromium(III) complexes can show phosphorescence from the spin-flip excited doublet states <sup>2</sup>E/<sup>2</sup>T<sub>1</sub> in the near-infrared with high photoluminescence quantum yields and extremely long lifetimes in the absence of dioxygen. The prototype molecular ruby, [Cr(ddpd)2]3+ (ddpd = <i>N</i>,<i>N</i>'-dimethyl-<i>N</i>,<i>N</i>'-dipyridine-2-ylpyridine-2,6-diamine), has a photoluminescence quantum yield and a luminescence lifetime of 13.7% and 1.1 ms in deaerated acetonitrile, respectively. However, its luminescence is strongly quenched by <sup>3</sup>O<sub>2</sub><i>via</i> an efficient Dexter-type energy transfer process. To enable luminescence applications of molecular rubies in solution under aerobic conditions, we explored the potential of sterically demanding ddpd ligands to shield the chromium(III) center from O<sub>2</sub> using steady state and time-resolved photoluminescence spectroscopy. The structures of the novel complexes with sterically demanding ligands were investigated by single crystal X-ray diffraction and quantum chemically by density functional theory calculations. The O<sub>2</sub> sensitivity of the photoluminescence was derived from absolutely measured photoluminescence quantum yields and excited state lifetimes under inert and aerobic conditions and by Stern-Volmer analyses of these data. Optimal sterically shielded chromium(III) complexes revealed photoluminescence quantum yields of up to 5.1% and excited state lifetimes of 518 µs in air-saturated acetonitrile, underlining the large potential of this ligand design approach to broaden the applicability of highly emissive chromium(III) complexes.
Addresses
  • Department of Chemistry, Johannes Gutenberg University of Mainz, Mainz, Germany. katja.heinze@uni-mainz.de.
Autoren
  • Laura Stein
  • Cui Wang
  • Christoph Förster
  • Ute Resch-Genger
  • Katja Heinze
DOI
10.1039/d2dt02950b
eISSN
1477-9234
Externe Identifier
  • PubMed Identifier: 36342442
Funding acknowledgements
  • Deutsche Forschungsgemeinschaft: RE 1203/23-1
  • Deutsche Forschungsgemeinschaft: RE 1203/23-2
  • Deutsche Forschungsgemeinschaft: INST 247/1018-1 FUGG
  • Deutsche Forschungsgemeinschaft: HE 2778/10-2
Open access
false
ISSN
1477-9226
Ausgabe der Veröffentlichung
46
Zeitschrift
Dalton transactions (Cambridge, England : 2003)
Sprache
eng
Medium
Electronic
Online publication date
2022
Paginierung
17664 - 17670
Datum der Veröffentlichung
2022
Status
Published
Publisher licence
CC BY-NC
Datum der Datenerfassung
2022
Titel
Bulky ligands protect molecular ruby from oxygen quenching.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
51

Data source: Europe PubMed Central

Abstract
Chromium(III) complexes can show phosphorescence from the spin-flip excited doublet states 2E/2T1 in the near-infrared with high photoluminescence quantum yields and extremely long lifetimes in the absence of dioxygen. The prototype molecular ruby, [Cr(ddpd)2]3+ (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine), has a photoluminescence quantum yield and a luminescence lifetime of 13.7% and 1.1 ms in deaerated acetonitrile, respectively. However, its luminescence is strongly quenched by 3O2via an efficient Dexter-type energy transfer process. To enable luminescence applications of molecular rubies in solution under aerobic conditions, we explored the potential of sterically demanding ddpd ligands to shield the chromium(III) center from O2 using steady state and time-resolved photoluminescence spectroscopy. The structures of the novel complexes with sterically demanding ligands were investigated by single crystal X-ray diffraction and quantum chemically by density functional theory calculations. The O2 sensitivity of the photoluminescence was derived from absolutely measured photoluminescence quantum yields and excited state lifetimes under inert and aerobic conditions and by Stern-Volmer analyses of these data. Optimal sterically shielded chromium(III) complexes revealed photoluminescence quantum yields of up to 5.1% and excited state lifetimes of 518 µs in air-saturated acetonitrile, underlining the large potential of this ligand design approach to broaden the applicability of highly emissive chromium(III) complexes.
Autoren
  • Laura Stein
  • Cui Wang
  • Christoph Förster
  • Ute Resch-Genger
  • Katja Heinze
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/36342442
DOI
10.1039/d2dt02950b
eISSN
1477-9234
Ausgabe der Veröffentlichung
46
Zeitschrift
Dalton Trans
Sprache
eng
Country
England
Paginierung
17664 - 17670
Datum der Veröffentlichung
2022
Status
Published online
Titel
Bulky ligands protect molecular ruby from oxygen quenching.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
51

Data source: PubMed

Author's licence
CC-BY-NC
Autoren
  • Laura Stein
  • Cui Wang
  • Christoph Förster
  • Ute Resch-Genger
  • Katja Heinze
Hosting institution
Universitätsbibliothek Mainz
Sammlungen
  • DFG-491381577-H
Resource version
Published version
DOI
10.1039/D2DT02950B
File(s) embargoed
false
Open access
true
ISSN
1477-9226
Ausgabe der Veröffentlichung
46
Zeitschrift
Dalton transactions
Schlüsselwörter
  • 540 Chemie
  • 540 Chemistry and allied sciences
Sprache
eng
Open access status
Open Access
Paginierung
17664 - 17670
Datum der Veröffentlichung
2022
Public URL
https://openscience.ub.uni-mainz.de/handle/20.500.12030/10304
Herausgeber
RSC
Datum der Datenerfassung
2024
Datum, an dem der Datensatz öffentlich gemacht wurde
2024
Zugang
Public
Titel
Bulky ligands protect molecular ruby from oxygen quenching
Ausgabe der Zeitschrift
51

Files

bulky_ligands_protect_molecul-20240417103700382.pdf

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