Excited State Tuning of Bis(tridentate) Ruthenium(II) Polypyridine Chromophores by Push-Pull Effects and Bite Angle Optimization: A Comprehensive Experimental and Theoretical Study

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Aaron Breivogel
  • Michael Meister
  • Christoph Foerster
  • Frederic Laquai
  • Katja Heinze
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000325135800021&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1002/chem.201302231
eISSN
1521-3765
Externe Identifier
  • Clarivate Analytics Document Solution ID: 227SW
  • PubMed Identifier: 24000040
ISSN
0947-6539
Ausgabe der Veröffentlichung
41
Zeitschrift
CHEMISTRY-A EUROPEAN JOURNAL
Schlüsselwörter
  • density functional calculations
  • excited states
  • ligands
  • luminescence
  • ruthenium
Paginierung
13745 - 13760
Datum der Veröffentlichung
2013
Status
Published
Titel
Excited State Tuning of Bis(tridentate) Ruthenium(II) Polypyridine Chromophores by Push-Pull Effects and Bite Angle Optimization: A Comprehensive Experimental and Theoretical Study
Sub types
  • Article
Ausgabe der Zeitschrift
19

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Abstract
<jats:title>Abstract</jats:title><jats:p>The synergy of push–pull substitution and enlarged ligand bite angles has been used in functionalized heteroleptic bis(tridentate) polypyridine complexes of ruthenium(II) to shift the <jats:sup>1</jats:sup>MLCT absorption and the <jats:sup>3</jats:sup>MLCT emission to lower energy, enhance the emission quantum yield, and to prolong the <jats:sup>3</jats:sup>MLCT excited‐state lifetime. In these complexes, that is, [Ru(ddpd)(EtOOC‐tpy)][PF<jats:sub>6</jats:sub>]<jats:sub>2</jats:sub>, [Ru(ddpd‐NH<jats:sub>2</jats:sub>)(EtOOC‐tpy)][PF<jats:sub>6</jats:sub>]<jats:sub>2</jats:sub>, [Ru(ddpd){(MeOOC)<jats:sub>3</jats:sub>‐tpy}][PF<jats:sub>6</jats:sub>]<jats:sub>2</jats:sub>, and [Ru(ddpd‐NH<jats:sub>2</jats:sub>){(EtOOC)<jats:sub>3</jats:sub>‐tpy}][PF<jats:sub>6</jats:sub>]<jats:sub>2</jats:sub> the combination of the electron‐accepting 2,2′;6′,2′′‐terpyridine (tpy) ligand equipped with one or three COOR substituents with the electron‐donating <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 (ddpd) ligand decorated with none or one NH<jats:sub>2</jats:sub> group enforces spatially separated and orthogonal frontier orbitals with a small HOMO–LUMO gap resulting in low‐energy <jats:sup>1</jats:sup>MLCT and <jats:sup>3</jats:sup>MLCT states. The extended bite angle of the ddpd ligand increases the ligand field splitting and pushes the deactivating <jats:sup>3</jats:sup>MC state to higher energy. The properties of the new isomerically pure mixed ligand complexes have been studied by using electrochemistry, UV/Vis absorption spectroscopy, static and time‐resolved luminescence spectroscopy, and transient absorption spectroscopy. The experimental data were rationalized by using density functional calculations on differently charged species (charge <jats:italic>n</jats:italic>=0–4) and on triplet excited states (<jats:sup>3</jats:sup>MLCT and <jats:sup>3</jats:sup>MC) as well as by time‐dependent density functional calculations (excited singlet states).</jats:p>
Autoren
  • Aaron Breivogel
  • Michael Meister
  • Christoph Förster
  • Frédéric Laquai
  • Katja Heinze
DOI
10.1002/chem.201302231
eISSN
1521-3765
ISSN
0947-6539
Ausgabe der Veröffentlichung
41
Zeitschrift
Chemistry – A European Journal
Sprache
en
Online publication date
2013
Paginierung
13745 - 13760
Datum der Veröffentlichung
2013
Status
Published
Herausgeber
Wiley
Herausgeber URL
http://dx.doi.org/10.1002/chem.201302231
Datum der Datenerfassung
2023
Titel
Excited State Tuning of Bis(tridentate) Ruthenium(II) Polypyridine Chromophores by Push–Pull Effects and Bite Angle Optimization: A Comprehensive Experimental and Theoretical Study
Ausgabe der Zeitschrift
19

Datenquelle: Crossref

Abstract
The synergy of push-pull substitution and enlarged ligand bite angles has been used in functionalized heteroleptic bis(tridentate) polypyridine complexes of ruthenium(II) to shift the (1) MLCT absorption and the (3) MLCT emission to lower energy, enhance the emission quantum yield, and to prolong the (3) MLCT excited-state lifetime. In these complexes, that is, [Ru(ddpd)(EtOOC-tpy)][PF6 ]2 , [Ru(ddpd-NH2 )(EtOOC-tpy)][PF6 ]2 , [Ru(ddpd){(MeOOC)3 -tpy}][PF6 ]2 , and [Ru(ddpd-NH2 ){(EtOOC)3 -tpy}][PF6 ]2 the combination of the electron-accepting 2,2';6',2''-terpyridine (tpy) ligand equipped with one or three COOR substituents with the electron-donating N,N'-dimethyl-N,N'-dipyridin-2-ylpyridine-2,6-diamine (ddpd) ligand decorated with none or one NH2 group enforces spatially separated and orthogonal frontier orbitals with a small HOMO-LUMO gap resulting in low-energy (1) MLCT and (3) MLCT states. The extended bite angle of the ddpd ligand increases the ligand field splitting and pushes the deactivating (3) MC state to higher energy. The properties of the new isomerically pure mixed ligand complexes have been studied by using electrochemistry, UV/Vis absorption spectroscopy, static and time-resolved luminescence spectroscopy, and transient absorption spectroscopy. The experimental data were rationalized by using density functional calculations on differently charged species (charge n=0-4) and on triplet excited states ((3) MLCT and (3) MC) as well as by time-dependent density functional calculations (excited singlet states).
Addresses
  • Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10-14, 55128 Mainz (Germany), Fax: (+49) 6131-39-27-277.
Autoren
  • Aaron Breivogel
  • Michael Meister
  • Christoph Förster
  • Frédéric Laquai
  • Katja Heinze
DOI
10.1002/chem.201302231
eISSN
1521-3765
Externe Identifier
  • PubMed Identifier: 24000040
Open access
false
ISSN
0947-6539
Ausgabe der Veröffentlichung
41
Zeitschrift
Chemistry (Weinheim an der Bergstrasse, Germany)
Sprache
eng
Medium
Print-Electronic
Online publication date
2013
Paginierung
13745 - 13760
Datum der Veröffentlichung
2013
Status
Published
Datum der Datenerfassung
2013
Titel
Excited state tuning of bis(tridentate) ruthenium(II) polypyridine chromophores by push-pull effects and bite angle optimization: a comprehensive experimental and theoretical study.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
19

Datenquelle: Europe PubMed Central

Abstract
The synergy of push-pull substitution and enlarged ligand bite angles has been used in functionalized heteroleptic bis(tridentate) polypyridine complexes of ruthenium(II) to shift the (1) MLCT absorption and the (3) MLCT emission to lower energy, enhance the emission quantum yield, and to prolong the (3) MLCT excited-state lifetime. In these complexes, that is, [Ru(ddpd)(EtOOC-tpy)][PF6 ]2 , [Ru(ddpd-NH2 )(EtOOC-tpy)][PF6 ]2 , [Ru(ddpd){(MeOOC)3 -tpy}][PF6 ]2 , and [Ru(ddpd-NH2 ){(EtOOC)3 -tpy}][PF6 ]2 the combination of the electron-accepting 2,2';6',2''-terpyridine (tpy) ligand equipped with one or three COOR substituents with the electron-donating N,N'-dimethyl-N,N'-dipyridin-2-ylpyridine-2,6-diamine (ddpd) ligand decorated with none or one NH2 group enforces spatially separated and orthogonal frontier orbitals with a small HOMO-LUMO gap resulting in low-energy (1) MLCT and (3) MLCT states. The extended bite angle of the ddpd ligand increases the ligand field splitting and pushes the deactivating (3) MC state to higher energy. The properties of the new isomerically pure mixed ligand complexes have been studied by using electrochemistry, UV/Vis absorption spectroscopy, static and time-resolved luminescence spectroscopy, and transient absorption spectroscopy. The experimental data were rationalized by using density functional calculations on differently charged species (charge n=0-4) and on triplet excited states ((3) MLCT and (3) MC) as well as by time-dependent density functional calculations (excited singlet states).
Autoren
  • Aaron Breivogel
  • Michael Meister
  • Christoph Förster
  • Frédéric Laquai
  • Katja Heinze
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/24000040
DOI
10.1002/chem.201302231
eISSN
1521-3765
Ausgabe der Veröffentlichung
41
Zeitschrift
Chemistry
Schlüsselwörter
  • density functional calculations
  • excited states
  • ligands
  • luminescence
  • ruthenium
Sprache
eng
Country
Germany
Paginierung
13745 - 13760
Datum der Veröffentlichung
2013
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2014
Titel
Excited state tuning of bis(tridentate) ruthenium(II) polypyridine chromophores by push-pull effects and bite angle optimization: a comprehensive experimental and theoretical study.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
19

Datenquelle: PubMed

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