Stable Molybdenum(0) Carbonyl Complex for Upconversion and Photoredox Catalysis
- Publication type:
- Journal article
- Metadata:
-
- Autoren
- Winald R Kitzmann
- Maria-Sophie Bertrams
- Pit Boden
- Alexander C Fischer
- Reneï Klauer
- Johannes Sutter
- Robert Naumann
- Christoph Foerster
- Gereon Niedner-Schatteburg
- Nicolas H Bings
- Johannes Hunger
- Christoph Kerzig
- Katja Heinze
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:001033856300001&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1021/jacs.3c03832
- eISSN
- 1520-5126
- Externe Identifier
- Clarivate Analytics Document Solution ID: N6XV4
- PubMed Identifier: 37478053
- ISSN
- 0002-7863
- Ausgabe der Veröffentlichung
- 30
- Zeitschrift
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- Paginierung
- 16597 - 16609
- Datum der Veröffentlichung
- 2023
- Status
- Published
- Titel
- Stable Molybdenum(0) Carbonyl Complex for Upconversion and Photoredox Catalysis
- Sub types
- Article
- Ausgabe der Zeitschrift
- 145
Data source: Web of Science (Lite)
- Other metadata sources:
-
- Autoren
- Winald R Kitzmann
- Maria-Sophie Bertrams
- Pit Boden
- Alexander C Fischer
- René Klauer
- Johannes Sutter
- Robert Naumann
- Christoph Förster
- Gereon Niedner-Schatteburg
- Nicolas H Bings
- Johannes Hunger
- Christoph Kerzig
- Katja Heinze
- DOI
- 10.1021/jacs.3c03832
- eISSN
- 1520-5126
- ISSN
- 0002-7863
- Ausgabe der Veröffentlichung
- 30
- Zeitschrift
- Journal of the American Chemical Society
- Sprache
- en
- Online publication date
- 2023
- Paginierung
- 16597 - 16609
- Datum der Veröffentlichung
- 2023
- Status
- Published
- Herausgeber
- American Chemical Society (ACS)
- Herausgeber URL
- http://dx.doi.org/10.1021/jacs.3c03832
- Datum der Datenerfassung
- 2023
- Titel
- Stable Molybdenum(0) Carbonyl Complex for Upconversion and Photoredox Catalysis
- Ausgabe der Zeitschrift
- 145
Data source: Crossref
- Abstract
- Photoactive complexes with earth-abundant metals have attracted increasing interest in the recent years fueled by the promise of sustainable photochemistry. However, sophisticated ligands with complicated syntheses are oftentimes required to enable photoactivity with nonprecious metals. Here, we combine a cheap metal with simple ligands to easily access a photoactive complex. Specifically, we synthesize the molybdenum(0) carbonyl complex Mo(CO)<sub>3</sub>(tpe) featuring the tripodal ligand 1,1,1-tris(pyrid-2-yl)ethane (tpe) in two steps with a high overall yield. The complex shows intense deep-red phosphorescence with excited state lifetimes of several hundred nanoseconds. Time-resolved infrared spectroscopy and laser flash photolysis reveal a triplet metal-to-ligand charge-transfer (<sup>3</sup>MLCT) state as the lowest excited state. Temperature-dependent luminescence complemented by density functional theory (DFT) calculations suggest thermal deactivation of the <sup>3</sup>MLCT state via higher lying metal-centered states in analogy to the well-known photophysics of [Ru(bpy)<sub>3</sub>]<sup>2+</sup>. Importantly, we found that the title compound is very photostable due to the lack of labilized Mo-CO bonds (as caused by <i>trans</i>-coordinated CO) in the facial configuration of the ligands. Finally, we show the versatility of the molybdenum(0) complex in two applications: (1) green-to-blue photon upconversion via a triplet-triplet annihilation mechanism and (2) photoredox catalysis for a green-light-driven dehalogenation reaction. Overall, our results establish tripodal carbonyl complexes as a promising design strategy to access stable photoactive complexes of nonprecious metals avoiding tedious multistep syntheses.
- Addresses
- Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
- Autoren
- Winald R Kitzmann
- Maria-Sophie Bertrams
- Pit Boden
- Alexander C Fischer
- René Klauer
- Johannes Sutter
- Robert Naumann
- Christoph Förster
- Gereon Niedner-Schatteburg
- Nicolas H Bings
- Johannes Hunger
- Christoph Kerzig
- Katja Heinze
- DOI
- 10.1021/jacs.3c03832
- eISSN
- 1520-5126
- Externe Identifier
- PubMed Identifier: 37478053
- Funding acknowledgements
- Fonds der Chemischen Industrie:
- Deutsche Forschungsgemeinschaft: INST 247/1018-1 FUGG
- Deutsche Forschungsgemeinschaft: KE 2313/3-1
- Max Planck Graduate Center mit der Johannes Gutenberg-Universit?t Mainz GmbH:
- Open access
- false
- ISSN
- 0002-7863
- Ausgabe der Veröffentlichung
- 30
- Zeitschrift
- Journal of the American Chemical Society
- Sprache
- eng
- Medium
- Print-Electronic
- Online publication date
- 2023
- Paginierung
- 16597 - 16609
- Datum der Veröffentlichung
- 2023
- Status
- Published
- Datum der Datenerfassung
- 2023
- Titel
- Stable Molybdenum(0) Carbonyl Complex for Upconversion and Photoredox Catalysis.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 145
Data source: Europe PubMed Central
- Abstract
- Photoactive complexes with earth-abundant metals have attracted increasing interest in the recent years fueled by the promise of sustainable photochemistry. However, sophisticated ligands with complicated syntheses are oftentimes required to enable photoactivity with nonprecious metals. Here, we combine a cheap metal with simple ligands to easily access a photoactive complex. Specifically, we synthesize the molybdenum(0) carbonyl complex Mo(CO)3(tpe) featuring the tripodal ligand 1,1,1-tris(pyrid-2-yl)ethane (tpe) in two steps with a high overall yield. The complex shows intense deep-red phosphorescence with excited state lifetimes of several hundred nanoseconds. Time-resolved infrared spectroscopy and laser flash photolysis reveal a triplet metal-to-ligand charge-transfer (3MLCT) state as the lowest excited state. Temperature-dependent luminescence complemented by density functional theory (DFT) calculations suggest thermal deactivation of the 3MLCT state via higher lying metal-centered states in analogy to the well-known photophysics of [Ru(bpy)3]2+. Importantly, we found that the title compound is very photostable due to the lack of labilized Mo-CO bonds (as caused by trans-coordinated CO) in the facial configuration of the ligands. Finally, we show the versatility of the molybdenum(0) complex in two applications: (1) green-to-blue photon upconversion via a triplet-triplet annihilation mechanism and (2) photoredox catalysis for a green-light-driven dehalogenation reaction. Overall, our results establish tripodal carbonyl complexes as a promising design strategy to access stable photoactive complexes of nonprecious metals avoiding tedious multistep syntheses.
- Autoren
- Winald R Kitzmann
- Maria-Sophie Bertrams
- Pit Boden
- Alexander C Fischer
- René Klauer
- Johannes Sutter
- Robert Naumann
- Christoph Förster
- Gereon Niedner-Schatteburg
- Nicolas H Bings
- Johannes Hunger
- Christoph Kerzig
- Katja Heinze
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/37478053
- DOI
- 10.1021/jacs.3c03832
- eISSN
- 1520-5126
- Ausgabe der Veröffentlichung
- 30
- Zeitschrift
- J Am Chem Soc
- Sprache
- eng
- Country
- United States
- Paginierung
- 16597 - 16609
- Datum der Veröffentlichung
- 2023
- Status
- Published
- Titel
- Stable Molybdenum(0) Carbonyl Complex for Upconversion and Photoredox Catalysis.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 145
Data source: PubMed
- Beziehungen:
-