Strongly Red-Emissive Molecular Ruby [Cr(bpmp)2]3+ Surpasses [Ru(bpy)3]2+
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Florian Reichenauer
- Cui Wang
- Christoph Forster
- Pit Boden
- Naz Ugur
- Ricardo Baez-Cruz
- Jens Kalmbach
- Luca M Carrella
- Eva Rentschler
- Charusheela Ramanan
- Gereon Niedner-Schatteburg
- Markus Gerhards
- Michael Seitz
- Ute Resch-Genger
- Katja Heinze
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000684586600056&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1021/jacs.1c05971
- eISSN
- 1520-5126
- Externe Identifier
- Clarivate Analytics Document Solution ID: TZ6ND
- PubMed Identifier: 34296865
- ISSN
- 0002-7863
- Ausgabe der Veröffentlichung
- 30
- Zeitschrift
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- Paginierung
- 11843 - 11855
- Datum der Veröffentlichung
- 2021
- Status
- Published
- Titel
- Strongly Red-Emissive Molecular Ruby [Cr(bpmp)<sub>2</sub>]<SUP>3+</SUP> Surpasses [Ru(bpy)<sub>3</sub>]<SUP>2+</SUP>
- Sub types
- Article
- Ausgabe der Zeitschrift
- 143
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Autoren
- Florian Reichenauer
- Cui Wang
- Christoph Förster
- Pit Boden
- Naz Ugur
- Ricardo Báez-Cruz
- Jens Kalmbach
- Luca M Carrella
- Eva Rentschler
- Charusheela Ramanan
- Gereon Niedner-Schatteburg
- Markus Gerhards
- Michael Seitz
- Ute Resch-Genger
- Katja Heinze
- DOI
- 10.1021/jacs.1c05971
- eISSN
- 1520-5126
- ISSN
- 0002-7863
- Ausgabe der Veröffentlichung
- 30
- Zeitschrift
- Journal of the American Chemical Society
- Sprache
- en
- Online publication date
- 2021
- Paginierung
- 11843 - 11855
- Datum der Veröffentlichung
- 2021
- Status
- Published
- Herausgeber
- American Chemical Society (ACS)
- Herausgeber URL
- http://dx.doi.org/10.1021/jacs.1c05971
- Datum der Datenerfassung
- 2023
- Titel
- Strongly Red-Emissive Molecular Ruby [Cr(bpmp)<sub>2</sub>]<sup>3+</sup> Surpasses [Ru(bpy)<sub>3</sub>]<sup>2+</sup>
- Ausgabe der Zeitschrift
- 143
Datenquelle: Crossref
- Abstract
- Gaining chemical control over the thermodynamics and kinetics of photoexcited states is paramount to an efficient and sustainable utilization of photoactive transition metal complexes in a plethora of technologies. In contrast to energies of charge transfer states described by spatially separated orbitals, the energies of spin-flip states cannot straightforwardly be predicted as Pauli repulsion and the nephelauxetic effect play key roles. Guided by multireference quantum chemical calculations, we report a novel highly luminescent spin-flip emitter with a quantum chemically predicted blue-shifted luminescence. The spin-flip emission band of the chromium complex [Cr(bpmp)<sub>2</sub>]<sup>3+</sup> (bpmp = 2,6-bis(2-pyridylmethyl)pyridine) shifted to higher energy from ca. 780 nm observed for known highly emissive chromium(III) complexes to 709 nm. The photoluminescence quantum yields climb to 20%, and very long excited state lifetimes in the millisecond range are achieved at room temperature in acidic D<sub>2</sub>O solution. Partial ligand deuteration increases the quantum yield to 25%. The high excited state energy of [Cr(bpmp)<sub>2</sub>]<sup>3+</sup> and its facile reduction to [Cr(bpmp)<sub>2</sub>]<sup>2+</sup> result in a high excited state redox potential. The ligand's methylene bridge acts as a Brønsted acid quenching the luminescence at high pH. Combined with a pH-insensitive chromium(III) emitter, ratiometric optical pH sensing is achieved with single wavelength excitation. The photophysical and ground state properties (quantum yield, lifetime, redox potential, and acid/base) of this spin-flip complex incorporating an earth-abundant metal surpass those of the classical precious metal [Ru(α-diimine)<sub>3</sub>]<sup>2+</sup> charge transfer complexes, which are commonly employed in optical sensing and photo(redox) catalysis, underlining the bright future of these molecular ruby analogues.
- Addresses
- Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
- Autoren
- Florian Reichenauer
- Cui Wang
- Christoph Förster
- Pit Boden
- Naz Ugur
- Ricardo Báez-Cruz
- Jens Kalmbach
- Luca M Carrella
- Eva Rentschler
- Charusheela Ramanan
- Gereon Niedner-Schatteburg
- Markus Gerhards
- Michael Seitz
- Ute Resch-Genger
- Katja Heinze
- DOI
- 10.1021/jacs.1c05971
- eISSN
- 1520-5126
- Externe Identifier
- PubMed Identifier: 34296865
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft: GE 961/10-1
- Deutsche Forschungsgemeinschaft: HE 2778/15-1
- Deutsche Forschungsgemeinschaft: RE 1203/23-1
- Deutsche Forschungsgemeinschaft: SE 1448/8-1
- 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
- 2021
- Paginierung
- 11843 - 11855
- Datum der Veröffentlichung
- 2021
- Status
- Published
- Publisher licence
- CC BY-NC-ND
- Datum der Datenerfassung
- 2021
- Titel
- Strongly Red-Emissive Molecular Ruby [Cr(bpmp)<sub>2</sub>]<sup>3+</sup> Surpasses [Ru(bpy)<sub>3</sub>]<sup>2</sup>.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 143
Datenquelle: Europe PubMed Central
- Abstract
- Gaining chemical control over the thermodynamics and kinetics of photoexcited states is paramount to an efficient and sustainable utilization of photoactive transition metal complexes in a plethora of technologies. In contrast to energies of charge transfer states described by spatially separated orbitals, the energies of spin-flip states cannot straightforwardly be predicted as Pauli repulsion and the nephelauxetic effect play key roles. Guided by multireference quantum chemical calculations, we report a novel highly luminescent spin-flip emitter with a quantum chemically predicted blue-shifted luminescence. The spin-flip emission band of the chromium complex [Cr(bpmp)2]3+ (bpmp = 2,6-bis(2-pyridylmethyl)pyridine) shifted to higher energy from ca. 780 nm observed for known highly emissive chromium(III) complexes to 709 nm. The photoluminescence quantum yields climb to 20%, and very long excited state lifetimes in the millisecond range are achieved at room temperature in acidic D2O solution. Partial ligand deuteration increases the quantum yield to 25%. The high excited state energy of [Cr(bpmp)2]3+ and its facile reduction to [Cr(bpmp)2]2+ result in a high excited state redox potential. The ligand's methylene bridge acts as a Brønsted acid quenching the luminescence at high pH. Combined with a pH-insensitive chromium(III) emitter, ratiometric optical pH sensing is achieved with single wavelength excitation. The photophysical and ground state properties (quantum yield, lifetime, redox potential, and acid/base) of this spin-flip complex incorporating an earth-abundant metal surpass those of the classical precious metal [Ru(α-diimine)3]2+ charge transfer complexes, which are commonly employed in optical sensing and photo(redox) catalysis, underlining the bright future of these molecular ruby analogues.
- Autoren
- Florian Reichenauer
- Cui Wang
- Christoph Förster
- Pit Boden
- Naz Ugur
- Ricardo Báez-Cruz
- Jens Kalmbach
- Luca M Carrella
- Eva Rentschler
- Charusheela Ramanan
- Gereon Niedner-Schatteburg
- Markus Gerhards
- Michael Seitz
- Ute Resch-Genger
- Katja Heinze
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/34296865
- DOI
- 10.1021/jacs.1c05971
- eISSN
- 1520-5126
- Ausgabe der Veröffentlichung
- 30
- Zeitschrift
- J Am Chem Soc
- Sprache
- eng
- Country
- United States
- Paginierung
- 11843 - 11855
- Datum der Veröffentlichung
- 2021
- Status
- Published
- Titel
- Strongly Red-Emissive Molecular Ruby [Cr(bpmp)2]3+ Surpasses [Ru(bpy)3]2.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 143
Datenquelle: PubMed
- Beziehungen:
-