Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Matthias Dorn
  • Jens Kalmbach
  • Pit Boden
  • Ayla Kruse
  • Chahinez Dab
  • Christian Reber
  • Gereon Niedner-Schatteburg
  • Stefan Lochbrunner
  • Markus Gerhards
  • Michael Seitz
  • Katja Heinze
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000675508900001&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1039/d1sc02137k
eISSN
2041-6539
Externe Identifier
  • Clarivate Analytics Document Solution ID: UC5DH
  • PubMed Identifier: 34476059
ISSN
2041-6520
Ausgabe der Veröffentlichung
32
Zeitschrift
CHEMICAL SCIENCE
Paginierung
10780 - 10790
Datum der Veröffentlichung
2021
Status
Published
Titel
Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry
Sub types
  • Article
Ausgabe der Zeitschrift
12

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Abstract
<jats:p>Vanadium is an abundant and cheap metal but near-infrared luminescent vanadium complexes are extremely rare with largely unexplored photophysics and photochemistry. We delineate the photodynamics of VCl<jats:sub>3</jats:sub>(ddpd) to infer novel design strategies.</jats:p>
Autoren
  • Matthias Dorn
  • Jens Kalmbach
  • Pit Boden
  • Ayla Kruse
  • Chahinez Dab
  • Christian Reber
  • Gereon Niedner-Schatteburg
  • Stefan Lochbrunner
  • Markus Gerhards
  • Michael Seitz
  • Katja Heinze
DOI
10.1039/d1sc02137k
eISSN
2041-6539
ISSN
2041-6520
Ausgabe der Veröffentlichung
32
Zeitschrift
Chemical Science
Sprache
en
Online publication date
2021
Paginierung
10780 - 10790
Status
Published online
Herausgeber
Royal Society of Chemistry (RSC)
Herausgeber URL
http://dx.doi.org/10.1039/d1sc02137k
Datum der Datenerfassung
2024
Titel
Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(<scp>iii</scp>) complex I: synthesis, spectroscopy and static quantum chemistry
Ausgabe der Zeitschrift
12

Datenquelle: Crossref

Abstract
In spite of intense, recent research efforts, luminescent transition metal complexes with Earth-abundant metals are still very rare owing to the small ligand field splitting of 3d transition metal complexes and the resulting non-emissive low-energy metal-centered states. Low-energy excited states decay efficiently non-radiatively, so that near-infrared emissive transition metal complexes with 3d transition metals are even more challenging. We report that the heteroleptic pseudo-octahedral d<sup>2</sup>-vanadium(iii) complex VCl<sub>3</sub>(ddpd) (ddpd = <i>N</i>,<i>N</i>'-dimethyl-<i>N</i>,<i>N</i>'-dipyridine-2-yl-pyridine-2,6-diamine) shows near-infrared singlet → triplet spin-flip phosphorescence maxima at 1102, 1219 and 1256 nm with a lifetime of 0.5 μs at room temperature. Band splitting, ligand deuteration, excitation energy and temperature effects on the excited state dynamics will be discussed on slow and fast timescales using Raman, static and time-resolved photoluminescence, step-scan FTIR and fs-UV pump-vis probe spectroscopy as well as photolysis experiments in combination with static quantum chemical calculations. These results inform future design strategies for molecular materials of Earth-abundant metal ions exhibiting spin-flip luminescence and photoinduced metal-ligand bond homolysis.
Addresses
  • Department of Chemistry, Johannes Gutenberg University of Mainz Duesbergweg 10-14 55128 Mainz Germany katja.heinze@uni-mainz.de.
Autoren
  • Matthias Dorn
  • Jens Kalmbach
  • Pit Boden
  • Ayla Kruse
  • Chahinez Dab
  • Christian Reber
  • Gereon Niedner-Schatteburg
  • Stefan Lochbrunner
  • Markus Gerhards
  • Michael Seitz
  • Katja Heinze
DOI
10.1039/d1sc02137k
eISSN
2041-6539
Externe Identifier
  • PubMed Identifier: 34476059
  • PubMed Central ID: PMC8372323
Funding acknowledgements
  • Deutsche Forschungsgemeinschaft: SE 1448/8-1
  • Deutsche Forschungsgemeinschaft: HE 2778/15-1
  • Deutsche Forschungsgemeinschaft: GE 961/10-1
  • Fonds de recherche du Québec – Nature et technologies:
  • Deutsche Forschungsgemeinschaft: LO 714/11-1
  • Natural Sciences and Engineering Research Council of Canada:
Open access
true
ISSN
2041-6520
Ausgabe der Veröffentlichung
32
Zeitschrift
Chemical science
Sprache
eng
Medium
Electronic-eCollection
Online publication date
2021
Open access status
Open Access
Paginierung
10780 - 10790
Datum der Veröffentlichung
2021
Status
Published
Publisher licence
CC BY
Datum der Datenerfassung
2021
Titel
Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry.
Sub types
  • research-article
  • Journal Article
Ausgabe der Zeitschrift
12

Files

https://pubs.rsc.org/en/content/articlepdf/2021/sc/d1sc02137k https://europepmc.org/articles/PMC8372323?pdf=render

Datenquelle: Europe PubMed Central

Abstract
In spite of intense, recent research efforts, luminescent transition metal complexes with Earth-abundant metals are still very rare owing to the small ligand field splitting of 3d transition metal complexes and the resulting non-emissive low-energy metal-centered states. Low-energy excited states decay efficiently non-radiatively, so that near-infrared emissive transition metal complexes with 3d transition metals are even more challenging. We report that the heteroleptic pseudo-octahedral d2-vanadium(iii) complex VCl3(ddpd) (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) shows near-infrared singlet → triplet spin-flip phosphorescence maxima at 1102, 1219 and 1256 nm with a lifetime of 0.5 μs at room temperature. Band splitting, ligand deuteration, excitation energy and temperature effects on the excited state dynamics will be discussed on slow and fast timescales using Raman, static and time-resolved photoluminescence, step-scan FTIR and fs-UV pump-vis probe spectroscopy as well as photolysis experiments in combination with static quantum chemical calculations. These results inform future design strategies for molecular materials of Earth-abundant metal ions exhibiting spin-flip luminescence and photoinduced metal-ligand bond homolysis.
Date of acceptance
2021
Autoren
  • Matthias Dorn
  • Jens Kalmbach
  • Pit Boden
  • Ayla Kruse
  • Chahinez Dab
  • Christian Reber
  • Gereon Niedner-Schatteburg
  • Stefan Lochbrunner
  • Markus Gerhards
  • Michael Seitz
  • Katja Heinze
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/34476059
DOI
10.1039/d1sc02137k
Externe Identifier
  • PubMed Central ID: PMC8372323
ISSN
2041-6520
Ausgabe der Veröffentlichung
32
Zeitschrift
Chem Sci
Sprache
eng
Country
England
Paginierung
10780 - 10790
PII
d1sc02137k
Datum der Veröffentlichung
2021
Status
Published online
Titel
Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
12

Datenquelle: PubMed

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