The photochemistry of mono- and dinuclear cyclometalated bis(tridentate)ruthenium(II) complexes: dual excited state deactivation and dual emission
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Christoph Kreitner
- Katja Heinze
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000372608300028&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1039/c6dt00384b
- eISSN
- 1477-9234
- Externe Identifier
- Clarivate Analytics Document Solution ID: DH2IL
- PubMed Identifier: 26922835
- ISSN
- 1477-9226
- Ausgabe der Veröffentlichung
- 13
- Zeitschrift
- DALTON TRANSACTIONS
- Paginierung
- 5640 - 5658
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Titel
- The photochemistry of mono- and dinuclear cyclometalated bis(tridentate)ruthenium(II) complexes: dual excited state deactivation and dual emission
- Sub types
- Article
- Ausgabe der Zeitschrift
- 45
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Abstract
- <p>A low-energy <sup>3</sup>LL′CT state efficiently depopulates the emissive <sup>3</sup>MLCT state in cyclometalated [Ru(dpb-R)(tpy)]<sup>+</sup> complexes (dpbH = 1,3-di(2-pyridyl)benzene, tpy = 2,2′;6′,2′′-terpyridine).</p>
- Autoren
- Christoph Kreitner
- Katja Heinze
- DOI
- 10.1039/c6dt00384b
- eISSN
- 1477-9234
- ISSN
- 1477-9226
- Ausgabe der Veröffentlichung
- 13
- Zeitschrift
- Dalton Transactions
- Sprache
- en
- Online publication date
- 2016
- Paginierung
- 5640 - 5658
- Status
- Published online
- Herausgeber
- Royal Society of Chemistry (RSC)
- Herausgeber URL
- http://dx.doi.org/10.1039/c6dt00384b
- Datum der Datenerfassung
- 2024
- Titel
- The photochemistry of mono- and dinuclear cyclometalated bis(tridentate)ruthenium(<scp>ii</scp>) complexes: dual excited state deactivation and dual emission
- Ausgabe der Zeitschrift
- 45
Datenquelle: Crossref
- Abstract
- The synthesis and characterization of a series of weakly emissive mononuclear cyclometalated [Ru(dpb-R)(tpy)](+) complexes with functional groups R of varying electron-donating characters at the dpb ligand are described (dpbH = 1,3-di(2-pyridyl)benzene, tpy = 2,2';6',2''-terpyridine, 1(+): R = NHCOMe, 2(+): R = NH2, 3(+): R = COOEt, 4(+): R = COOH). Steady-state emission spectroscopy in the temperature range between 298 K and 77 K revealed a previously unrecognized excited state deactivation pathway via low-lying triplet ligand-to-ligand ((3)LL'CT) charge transfer states in addition to the well-known pathway via(3)MC states. Thermal activation barriers for depopulation of the emissive metal-to-ligand charge transfer ((3)MLCT) states via the (3)MC (metal-centered) and (3)LL'CT states were determined experimentally for complexes 1(+) and 3(+). The experimental results were further corroborated by calculating the respective (3)MLCT-(3)LL'CT and (3)MLCT-(3)MC transition states and their energies with density functional theoretical methods. The R substituent modifies the energy difference between the (3)MLCT and (3)LL'CT states and the corresponding activation barrier but leaves the analogous (3)MLCT/(3)MC energetics essentially untouched. Additionally, the dinuclear complex [(tpy)Ru(dpb-NHCO-dpb)Ru(tpy)](2+), 6(2+), containing a biscyclometalating bridge was devised. Despite the asymmetric nature induced by the amide bridge, the mixed-valent cation 6(3+) is ascribed to Robin-Day class II with a broad and intense intervalence charge-transfer (IVCT) absorption (λmax = 1165 nm). Upon optical excitation, the Ru(II)/Ru(II) complex 6(2+) exhibits dual emission in liquid solution from two independently emitting (3)MLCT states localized at the two remote [Ru(tpy)] fragments. No equilibration via Dexter energy transfer is possible due to their large distance and short excited state lifetimes.
- Addresses
- Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg University, Duesbergweg 10-14, D-55128 Mainz, Germany. katja.heinze@uni-mainz.de.
- Autoren
- Christoph Kreitner
- Katja Heinze
- DOI
- 10.1039/c6dt00384b
- eISSN
- 1477-9234
- Externe Identifier
- PubMed Identifier: 26922835
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft: GSC 266
- Open access
- false
- ISSN
- 1477-9226
- Ausgabe der Veröffentlichung
- 13
- Zeitschrift
- Dalton transactions (Cambridge, England : 2003)
- Sprache
- eng
- Medium
- Print-Electronic
- Online publication date
- 2016
- Paginierung
- 5640 - 5658
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Datum der Datenerfassung
- 2016
- Titel
- The photochemistry of mono- and dinuclear cyclometalated bis(tridentate)ruthenium(II) complexes: dual excited state deactivation and dual emission.
- Sub types
- Research Support, Non-U.S. Gov't
- Journal Article
- Ausgabe der Zeitschrift
- 45
Datenquelle: Europe PubMed Central
- Abstract
- The synthesis and characterization of a series of weakly emissive mononuclear cyclometalated [Ru(dpb-R)(tpy)](+) complexes with functional groups R of varying electron-donating characters at the dpb ligand are described (dpbH = 1,3-di(2-pyridyl)benzene, tpy = 2,2';6',2''-terpyridine, 1(+): R = NHCOMe, 2(+): R = NH2, 3(+): R = COOEt, 4(+): R = COOH). Steady-state emission spectroscopy in the temperature range between 298 K and 77 K revealed a previously unrecognized excited state deactivation pathway via low-lying triplet ligand-to-ligand ((3)LL'CT) charge transfer states in addition to the well-known pathway via(3)MC states. Thermal activation barriers for depopulation of the emissive metal-to-ligand charge transfer ((3)MLCT) states via the (3)MC (metal-centered) and (3)LL'CT states were determined experimentally for complexes 1(+) and 3(+). The experimental results were further corroborated by calculating the respective (3)MLCT-(3)LL'CT and (3)MLCT-(3)MC transition states and their energies with density functional theoretical methods. The R substituent modifies the energy difference between the (3)MLCT and (3)LL'CT states and the corresponding activation barrier but leaves the analogous (3)MLCT/(3)MC energetics essentially untouched. Additionally, the dinuclear complex [(tpy)Ru(dpb-NHCO-dpb)Ru(tpy)](2+), 6(2+), containing a biscyclometalating bridge was devised. Despite the asymmetric nature induced by the amide bridge, the mixed-valent cation 6(3+) is ascribed to Robin-Day class II with a broad and intense intervalence charge-transfer (IVCT) absorption (λmax = 1165 nm). Upon optical excitation, the Ru(II)/Ru(II) complex 6(2+) exhibits dual emission in liquid solution from two independently emitting (3)MLCT states localized at the two remote [Ru(tpy)] fragments. No equilibration via Dexter energy transfer is possible due to their large distance and short excited state lifetimes.
- Autoren
- Christoph Kreitner
- Katja Heinze
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/26922835
- DOI
- 10.1039/c6dt00384b
- eISSN
- 1477-9234
- Ausgabe der Veröffentlichung
- 13
- Zeitschrift
- Dalton Trans
- Sprache
- eng
- Country
- England
- Paginierung
- 5640 - 5658
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Datum, an dem der Datensatz öffentlich gemacht wurde
- 2016
- Titel
- The photochemistry of mono- and dinuclear cyclometalated bis(tridentate)ruthenium(II) complexes: dual excited state deactivation and dual emission.
- Sub types
- Journal Article
- Research Support, Non-U.S. Gov't
- Ausgabe der Zeitschrift
- 45
Datenquelle: PubMed
- Beziehungen:
-