Exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines
In this work, we report the evolution of the properties of the inter-valence charge transfer (IVCT) transition in a family of cyanide-bridged ruthenium polypyridines of general formula [RuII(tpy)(bpy)(μ-CN)RuIII(bpy)2(L)]3/4+ (tpy = 2,2′,6′,2′′-terpyridine; bpy = 2,2′-bipyridine; L = Cl-, NCS-, 4-di...
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2017
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v46_n45_p15757_Oviedo http://hdl.handle.net/20.500.12110/paper_14779226_v46_n45_p15757_Oviedo |
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paper:paper_14779226_v46_n45_p15757_Oviedo2023-06-08T16:18:17Z Exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines Acetonitrile Charge transfer Organic solvents Redox reactions 4-dimethylaminopyridine Cyanide-bridged Delocalized transition DFT calculation Electronic transition General formulas Intensity enhancement Redox potentials Ruthenium In this work, we report the evolution of the properties of the inter-valence charge transfer (IVCT) transition in a family of cyanide-bridged ruthenium polypyridines of general formula [RuII(tpy)(bpy)(μ-CN)RuIII(bpy)2(L)]3/4+ (tpy = 2,2′,6′,2′′-terpyridine; bpy = 2,2′-bipyridine; L = Cl-, NCS-, 4-dimethylaminopyridine or acetonitrile). In these complexes, the redox potential difference between both ruthenium centers (ΔE) is systematically modified. A decrease in ΔE causes a red shift of the energy and an intensity enhancement of the observed IVCT transitions. For L = acetonitrile, the IVCT band becomes narrower and asymmetrical, and shows very little dependence on the nature of the solvent, suggesting a delocalized configuration, although a non-symmetrical one. Also, additional electronic transitions of low energy are clearly resolved in this complex. The observed variation in the properties of the IVCT transitions can be understood on the basis of DFT calculations, that point to increasing mixing between the dπ orbitals of both Ru ions. © 2017 The Royal Society of Chemistry. 2017 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v46_n45_p15757_Oviedo http://hdl.handle.net/20.500.12110/paper_14779226_v46_n45_p15757_Oviedo |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Acetonitrile Charge transfer Organic solvents Redox reactions 4-dimethylaminopyridine Cyanide-bridged Delocalized transition DFT calculation Electronic transition General formulas Intensity enhancement Redox potentials Ruthenium |
| spellingShingle |
Acetonitrile Charge transfer Organic solvents Redox reactions 4-dimethylaminopyridine Cyanide-bridged Delocalized transition DFT calculation Electronic transition General formulas Intensity enhancement Redox potentials Ruthenium Exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines |
| topic_facet |
Acetonitrile Charge transfer Organic solvents Redox reactions 4-dimethylaminopyridine Cyanide-bridged Delocalized transition DFT calculation Electronic transition General formulas Intensity enhancement Redox potentials Ruthenium |
| description |
In this work, we report the evolution of the properties of the inter-valence charge transfer (IVCT) transition in a family of cyanide-bridged ruthenium polypyridines of general formula [RuII(tpy)(bpy)(μ-CN)RuIII(bpy)2(L)]3/4+ (tpy = 2,2′,6′,2′′-terpyridine; bpy = 2,2′-bipyridine; L = Cl-, NCS-, 4-dimethylaminopyridine or acetonitrile). In these complexes, the redox potential difference between both ruthenium centers (ΔE) is systematically modified. A decrease in ΔE causes a red shift of the energy and an intensity enhancement of the observed IVCT transitions. For L = acetonitrile, the IVCT band becomes narrower and asymmetrical, and shows very little dependence on the nature of the solvent, suggesting a delocalized configuration, although a non-symmetrical one. Also, additional electronic transitions of low energy are clearly resolved in this complex. The observed variation in the properties of the IVCT transitions can be understood on the basis of DFT calculations, that point to increasing mixing between the dπ orbitals of both Ru ions. © 2017 The Royal Society of Chemistry. |
| title |
Exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines |
| title_short |
Exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines |
| title_full |
Exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines |
| title_fullStr |
Exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines |
| title_full_unstemmed |
Exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines |
| title_sort |
exploring the localized to delocalized transition in non-symmetric bimetallic ruthenium polypyridines |
| publishDate |
2017 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v46_n45_p15757_Oviedo http://hdl.handle.net/20.500.12110/paper_14779226_v46_n45_p15757_Oviedo |
| _version_ |
1768541627148664832 |