Effects of Sequence, Connectivity, and Counter Ions in New Amide-Linked Ru(tpy)2-Re(bpy) Chromophores on Redox Chemistry and Photophysics

Publication type:
Journal article
Metadata:
Autoren
  • Jan Dietrich
  • Ute Thorenz
  • Christoph Foerster
  • Katja Heinze
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000314627700015&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1021/ic301632y
eISSN
1520-510X
Externe Identifier
  • Clarivate Analytics Document Solution ID: 085PW
  • PubMed Identifier: 23311446
ISSN
0020-1669
Ausgabe der Veröffentlichung
3
Zeitschrift
INORGANIC CHEMISTRY
Paginierung
1248 - 1264
Datum der Veröffentlichung
2013
Status
Published
Titel
Effects of Sequence, Connectivity, and Counter Ions in New Amide-Linked Ru(tpy)<sub>2</sub>-Re(bpy) Chromophores on Redox Chemistry and Photophysics
Sub types
  • Article
Ausgabe der Zeitschrift
52

Data source: Web of Science (Lite)

Other metadata sources:
Autoren
  • Jan Dietrich
  • Ute Thorenz
  • Christoph Förster
  • Katja Heinze
DOI
10.1021/ic301632y
eISSN
1520-510X
ISSN
0020-1669
Ausgabe der Veröffentlichung
3
Zeitschrift
Inorganic Chemistry
Sprache
en
Online publication date
2013
Paginierung
1248 - 1264
Datum der Veröffentlichung
2013
Status
Published
Herausgeber
American Chemical Society (ACS)
Herausgeber URL
http://dx.doi.org/10.1021/ic301632y
Datum der Datenerfassung
2023
Titel
Effects of Sequence, Connectivity, and Counter Ions in New Amide-Linked Ru(tpy)<sub>2</sub>–Re(bpy) Chromophores on Redox Chemistry and Photophysics
Ausgabe der Zeitschrift
52

Data source: Crossref

Abstract
New cationic metallo ligands L1-L3 based on bis(terpyridine) ruthenium(II) complexes decorated with differently substituted 2,2'-bipyridines attached via amide groups (5-NHCO-bpy, 4-CONH-bpy, 5-CONH-bpy) were prepared. Coordination of Re(I)Cl(CO)(3) fragments to the bpy unit gives the corresponding bimetallic Ru~Re complexes 1-3. Hydrogen bonds of the bridging amide groups to [PF(6)](-) counterions or to water molecules are observed both in the solid state and in solution. The impact of the amide orientation, the connecting site, and the coordination of counterions on redox and photophysical properties is explored. Both the metallo ligands L1-L3 and the bimetallic complexes 1-3 are emissive at room temperature in fluid solution. The emission originates from (3)MLCT(Ru) states in all cases. Accordingly, the first oxidation of L1-L3 and 1-3 to [L1](+)-[L3](+) and [1](+)-[3](+) is assigned to the Ru(II/III) couple, while the first reduction to [L1](-)-[L3](-) and [1](-)-[3](-) occurs at the tpy-CO ligand as shown by UV/vis, IR, and EPR spectroscopy of the chemically generated radicals. Under rapid freezing conditions, radicals [2](-) and [3](-) are stabilized as different valence isomers with the odd electron localized at the [bpy-CO](•) bridging unit instead of the [tpy-CO](•). Furthermore, in radical [3](-) this valence equilibrium is shifted from [bpy-CO](•) to [tpy-CO](•) by coordination of [PF(6)](-) counterions to the bridging amide unit and back by replacing the [PF(6)](-) counterion with [BPh(4)](-). Photoinduced electron transfer (λ(exc) = 500 nm) to L1-L3 and to 1-3 is successful using triethanolamine (TEOA) as a reducing agent. Photocatalytic reduction of CO(2) by TEOA and 1-3 is hampered by the wrong site of electron localization in the one-electron reduced species [1](-)-[3](-).
Addresses
  • Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
Autoren
  • Jan Dietrich
  • Ute Thorenz
  • Christoph Förster
  • Katja Heinze
DOI
10.1021/ic301632y
eISSN
1520-510X
Externe Identifier
  • PubMed Identifier: 23311446
Open access
false
ISSN
0020-1669
Ausgabe der Veröffentlichung
3
Zeitschrift
Inorganic chemistry
Schlüsselwörter
  • Ions
  • Rhenium
  • Ruthenium
  • Amides
  • Organometallic Compounds
  • Crystallography, X-Ray
  • Molecular Conformation
  • Oxidation-Reduction
  • Quantum Theory
  • Models, Molecular
  • Photochemical Processes
Sprache
eng
Medium
Print-Electronic
Online publication date
2013
Paginierung
1248 - 1264
Datum der Veröffentlichung
2013
Status
Published
Datum der Datenerfassung
2013
Titel
Effects of sequence, connectivity, and counter ions in new amide-linked Ru(tpy)2-Re(bpy) chromophores on redox chemistry and photophysics.
Sub types
  • Research Support, Non-U.S. Gov't
  • Journal Article
Ausgabe der Zeitschrift
52

Data source: Europe PubMed Central

Abstract
New cationic metallo ligands L1-L3 based on bis(terpyridine) ruthenium(II) complexes decorated with differently substituted 2,2'-bipyridines attached via amide groups (5-NHCO-bpy, 4-CONH-bpy, 5-CONH-bpy) were prepared. Coordination of Re(I)Cl(CO)(3) fragments to the bpy unit gives the corresponding bimetallic Ru~Re complexes 1-3. Hydrogen bonds of the bridging amide groups to [PF(6)](-) counterions or to water molecules are observed both in the solid state and in solution. The impact of the amide orientation, the connecting site, and the coordination of counterions on redox and photophysical properties is explored. Both the metallo ligands L1-L3 and the bimetallic complexes 1-3 are emissive at room temperature in fluid solution. The emission originates from (3)MLCT(Ru) states in all cases. Accordingly, the first oxidation of L1-L3 and 1-3 to [L1](+)-[L3](+) and [1](+)-[3](+) is assigned to the Ru(II/III) couple, while the first reduction to [L1](-)-[L3](-) and [1](-)-[3](-) occurs at the tpy-CO ligand as shown by UV/vis, IR, and EPR spectroscopy of the chemically generated radicals. Under rapid freezing conditions, radicals [2](-) and [3](-) are stabilized as different valence isomers with the odd electron localized at the [bpy-CO](•) bridging unit instead of the [tpy-CO](•). Furthermore, in radical [3](-) this valence equilibrium is shifted from [bpy-CO](•) to [tpy-CO](•) by coordination of [PF(6)](-) counterions to the bridging amide unit and back by replacing the [PF(6)](-) counterion with [BPh(4)](-). Photoinduced electron transfer (λ(exc) = 500 nm) to L1-L3 and to 1-3 is successful using triethanolamine (TEOA) as a reducing agent. Photocatalytic reduction of CO(2) by TEOA and 1-3 is hampered by the wrong site of electron localization in the one-electron reduced species [1](-)-[3](-).
Autoren
  • Jan Dietrich
  • Ute Thorenz
  • Christoph Förster
  • Katja Heinze
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/23311446
DOI
10.1021/ic301632y
eISSN
1520-510X
Ausgabe der Veröffentlichung
3
Zeitschrift
Inorg Chem
Schlüsselwörter
  • Amides
  • Crystallography, X-Ray
  • Ions
  • Models, Molecular
  • Molecular Conformation
  • Organometallic Compounds
  • Oxidation-Reduction
  • Photochemical Processes
  • Quantum Theory
  • Rhenium
  • Ruthenium
Sprache
eng
Country
United States
Paginierung
1248 - 1264
Datum der Veröffentlichung
2013
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2013
Titel
Effects of sequence, connectivity, and counter ions in new amide-linked Ru(tpy)2-Re(bpy) chromophores on redox chemistry and photophysics.
Sub types
  • Journal Article
  • Research Support, Non-U.S. Gov't
Ausgabe der Zeitschrift
52

Data source: PubMed

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