Molecular Rubies in Photoredox Catalysis
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Steven Sittel
- Robert Naumann
- Katja Heinze
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000807684600001&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.3389/fchem.2022.887439
- Externe Identifier
- Clarivate Analytics Document Solution ID: 1X8FO
- PubMed Identifier: 35464204
- ISSN
- 2296-2646
- Zeitschrift
- FRONTIERS IN CHEMISTRY
- Schlüsselwörter
- chromium
- radical cation
- Diels-Alder reaction
- [4+2] cycloaddition
- photoredox catalysis
- singlet oxygen
- Artikelnummer
- ARTN 887439
- Datum der Veröffentlichung
- 2022
- Status
- Published
- Titel
- Molecular Rubies in Photoredox Catalysis
- Sub types
- Article
- Ausgabe der Zeitschrift
- 10
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Abstract
- <jats:p>The molecular ruby <jats:bold>[Cr(tpe)</jats:bold><jats:sub><jats:bold>2</jats:bold></jats:sub><jats:bold>]</jats:bold><jats:sup><jats:bold>3+</jats:bold></jats:sup> and the tris(bipyridine) chromium(III) complex <jats:bold>[Cr(dmcbpy)</jats:bold><jats:sub><jats:bold>3</jats:bold></jats:sub><jats:bold>]</jats:bold><jats:sup><jats:bold>3+</jats:bold></jats:sup> as well as the tris(bipyrazine)ruthenium(II) complex <jats:bold>[Ru(bpz)</jats:bold><jats:sub><jats:bold>3</jats:bold></jats:sub><jats:bold>]</jats:bold><jats:sup><jats:bold>2+</jats:bold></jats:sup> were employed in the visible light-induced radical cation [4+2] cycloaddition (tpe = 1,1,1-tris(pyrid-2-yl)ethane, dmcbpy = 4,4′-dimethoxycarbonyl-2,2′-bipyridine, bpz = 2,2′-bipyrazine), while <jats:bold>[Cr(ddpd)</jats:bold><jats:sub><jats:bold>2</jats:bold></jats:sub><jats:bold>]</jats:bold><jats:sup><jats:bold>3+</jats:bold></jats:sup> serves as a control system (ddpd = <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>′-dimethyl-<jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>′-dipyridin-2-ylpyridine-2,6-diamine). Along with an updated mechanistic proposal for the Cr<jats:sup>III</jats:sup> driven catalytic cycle based on redox chemistry, Stern-Volmer analyses, UV/Vis/NIR spectroscopic and nanosecond laser flash photolysis studies, we demonstrate that the very weakly absorbing photocatalyst <jats:bold>[Cr(tpe)</jats:bold><jats:sub><jats:bold>2</jats:bold></jats:sub><jats:bold>]</jats:bold><jats:sup><jats:bold>3+</jats:bold></jats:sup> outcompetes <jats:bold>[Cr(dmcbpy)</jats:bold><jats:sub><jats:bold>3</jats:bold></jats:sub><jats:bold>]</jats:bold><jats:sup><jats:bold>3+</jats:bold></jats:sup> and even <jats:bold>[Ru(bpz)</jats:bold><jats:sub><jats:bold>3</jats:bold></jats:sub><jats:bold>]</jats:bold><jats:sup><jats:bold>2+</jats:bold></jats:sup> in particular at low catalyst loadings, which appears contradictory at first sight. The high photostability, the reversible redoxchemistry and the very long excited state lifetime account for the exceptional performance and even reusability of <jats:bold>[Cr(tpe)</jats:bold><jats:sub><jats:bold>2</jats:bold></jats:sub><jats:bold>]</jats:bold><jats:sup><jats:bold>3+</jats:bold></jats:sup> in this photoredox catalytic system.</jats:p>
- Autoren
- Steven Sittel
- Robert Naumann
- Katja Heinze
- DOI
- 10.3389/fchem.2022.887439
- eISSN
- 2296-2646
- Zeitschrift
- Frontiers in Chemistry
- Online publication date
- 2022
- Status
- Published online
- Herausgeber
- Frontiers Media SA
- Herausgeber URL
- http://dx.doi.org/10.3389/fchem.2022.887439
- Datum der Datenerfassung
- 2022
- Titel
- Molecular Rubies in Photoredox Catalysis
- Ausgabe der Zeitschrift
- 10
Datenquelle: Crossref
- Abstract
- The molecular ruby <b>[Cr(tpe)</b> <sub><b>2</b></sub> <b>]</b> <sup><b>3+</b></sup> and the tris(bipyridine) chromium(III) complex <b>[Cr(dmcbpy)</b> <sub><b>3</b></sub> <b>]</b> <sup><b>3+</b></sup> as well as the tris(bipyrazine)ruthenium(II) complex <b>[Ru(bpz)</b> <sub><b>3</b></sub> <b>]</b> <sup><b>2+</b></sup> were employed in the visible light-induced radical cation [4+2] cycloaddition (tpe = 1,1,1-tris(pyrid-2-yl)ethane, dmcbpy = 4,4'-dimethoxycarbonyl-2,2'-bipyridine, bpz = 2,2'-bipyrazine), while <b>[Cr(ddpd)</b> <sub><b>2</b></sub> <b>]</b> <sup><b>3+</b></sup> serves as a control system (ddpd = <i>N</i>,<i>N</i>'-dimethyl-<i>N</i>,<i>N</i>'-dipyridin-2-ylpyridine-2,6-diamine). Along with an updated mechanistic proposal for the Cr<sup>III</sup> driven catalytic cycle based on redox chemistry, Stern-Volmer analyses, UV/Vis/NIR spectroscopic and nanosecond laser flash photolysis studies, we demonstrate that the very weakly absorbing photocatalyst <b>[Cr(tpe)</b> <sub><b>2</b></sub> <b>]</b> <sup><b>3+</b></sup> outcompetes <b>[Cr(dmcbpy)</b> <sub><b>3</b></sub> <b>]</b> <sup><b>3+</b></sup> and even <b>[Ru(bpz)</b> <sub><b>3</b></sub> <b>]</b> <sup><b>2+</b></sup> in particular at low catalyst loadings, which appears contradictory at first sight. The high photostability, the reversible redoxchemistry and the very long excited state lifetime account for the exceptional performance and even reusability of <b>[Cr(tpe)</b> <sub><b>2</b></sub> <b>]</b> <sup><b>3+</b></sup> in this photoredox catalytic system.
- Addresses
- Department of Chemistry, Johannes Gutenberg University, Mainz, Germany.
- Autoren
- Steven Sittel
- Robert Naumann
- Katja Heinze
- DOI
- 10.3389/fchem.2022.887439
- eISSN
- 2296-2646
- Externe Identifier
- PubMed Identifier: 35464204
- PubMed Central ID: PMC9021569
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft: HE2778/10-2
- Open access
- true
- ISSN
- 2296-2646
- Zeitschrift
- Frontiers in chemistry
- Sprache
- eng
- Medium
- Electronic-eCollection
- Online publication date
- 2022
- Open access status
- Open Access
- Paginierung
- 887439
- Datum der Veröffentlichung
- 2022
- Status
- Published
- Publisher licence
- CC BY
- Datum der Datenerfassung
- 2022
- Titel
- Molecular Rubies in Photoredox Catalysis.
- Sub types
- research-article
- Journal Article
- Ausgabe der Zeitschrift
- 10
Files
https://www.frontiersin.org/articles/10.3389/fchem.2022.887439/pdf https://europepmc.org/articles/PMC9021569?pdf=render
Datenquelle: Europe PubMed Central
- Abstract
- The molecular ruby [Cr(tpe) 2 ] 3+ and the tris(bipyridine) chromium(III) complex [Cr(dmcbpy) 3 ] 3+ as well as the tris(bipyrazine)ruthenium(II) complex [Ru(bpz) 3 ] 2+ were employed in the visible light-induced radical cation [4+2] cycloaddition (tpe = 1,1,1-tris(pyrid-2-yl)ethane, dmcbpy = 4,4'-dimethoxycarbonyl-2,2'-bipyridine, bpz = 2,2'-bipyrazine), while [Cr(ddpd) 2 ] 3+ serves as a control system (ddpd = N,N'-dimethyl-N,N'-dipyridin-2-ylpyridine-2,6-diamine). Along with an updated mechanistic proposal for the CrIII driven catalytic cycle based on redox chemistry, Stern-Volmer analyses, UV/Vis/NIR spectroscopic and nanosecond laser flash photolysis studies, we demonstrate that the very weakly absorbing photocatalyst [Cr(tpe) 2 ] 3+ outcompetes [Cr(dmcbpy) 3 ] 3+ and even [Ru(bpz) 3 ] 2+ in particular at low catalyst loadings, which appears contradictory at first sight. The high photostability, the reversible redoxchemistry and the very long excited state lifetime account for the exceptional performance and even reusability of [Cr(tpe) 2 ] 3+ in this photoredox catalytic system.
- Date of acceptance
- 2022
- Autoren
- Steven Sittel
- Robert Naumann
- Katja Heinze
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/35464204
- DOI
- 10.3389/fchem.2022.887439
- Externe Identifier
- PubMed Central ID: PMC9021569
- ISSN
- 2296-2646
- Zeitschrift
- Front Chem
- Schlüsselwörter
- Diels-Alder reaction
- [4+2] cycloaddition
- chromium
- photoredox catalysis
- radical cation
- singlet oxygen
- Sprache
- eng
- Country
- Switzerland
- Paginierung
- 887439
- PII
- 887439
- Datum der Veröffentlichung
- 2022
- Status
- Published online
- Titel
- Molecular Rubies in Photoredox Catalysis.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 10
Datenquelle: PubMed
- Author's licence
- CC-BY
- Autoren
- Steven Sittel
- Robert Naumann
- Katja Heinze
- Hosting institution
- Universitätsbibliothek Mainz
- Sammlungen
- DFG-491381577-G
- Resource version
- Published version
- DOI
- 10.3389/fchem.2022.887439
- Funding acknowledgements
- Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 491381577
- File(s) embargoed
- false
- Open access
- true
- ISSN
- 2296-2646
- Zeitschrift
- Frontiers in chemistry
- Schlüsselwörter
- 540 Chemie
- 540 Chemistry and allied sciences
- Sprache
- eng
- Open access status
- Open Access
- Paginierung
- 887439
- Datum der Veröffentlichung
- 2022
- Public URL
- https://openscience.ub.uni-mainz.de/handle/20.500.12030/8213
- Herausgeber
- Frontiers Media
- Datum der Datenerfassung
- 2022
- Datum, an dem der Datensatz öffentlich gemacht wurde
- 2022
- Zugang
- Public
- Titel
- Molecular rubies in photoredox catalysis
- Ausgabe der Zeitschrift
- 10
Files
molecular_rubies_in_photoredo-20221028152436261.pdf molecular_rubies_in_photoredo-20221102113317036.PDF
Datenquelle: OPENSCIENCE.UB
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