Tuning of the Reorganization Energies by Innocent Co-ligands in Novel Mixed-Valent Dinuclear Ruthenium Complexes
Two novel mixed-valent ruthenium complexes, of formulae [(tpy)(bpy)RuII(pz)RuIII(edta)]+ and [(CN)4RuII(bpz)RuIII(edta)]3- (where tpy = 2,2′:6′,2″-terpyridine, bpy = 2,2′-bipyridine, pz = pyrazine, bpz = 2,2′-bipyrazine, edta = ethylenediaminetetraacetate), were prepared and spectroscopically charac...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2003 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/62219 |
| Acceso en línea: | http://hdl.handle.net/11336/62219 |
| Access Level: | acceso abierto |
| Palabra clave: | Energy Conversion Intramolecular Electron Transfer Inverted Region Mixed-Valence Reorganization Energies Ruthenium Complexes https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | Two novel mixed-valent ruthenium complexes, of formulae [(tpy)(bpy)RuII(pz)RuIII(edta)]+ and [(CN)4RuII(bpz)RuIII(edta)]3- (where tpy = 2,2′:6′,2″-terpyridine, bpy = 2,2′-bipyridine, pz = pyrazine, bpz = 2,2′-bipyrazine, edta = ethylenediaminetetraacetate), were prepared and spectroscopically characterized in aqueous solutions and as solid salts with suitable counterions. For comparison purposes, two new ruthenium complexes: a dinuclear species, of formula [(CN)4RuII(bpz)RuII (NH3)5], and a trinuclear species, of formula {(CN)4RuII(bpz)[RuII (NH3)5]2}2+, were also prepared and characterized in aqueous solutions. From spectral data of metal-to-metal charge transfer (MMCT) absorption bands, a Hush analysis was made, and the reorganization energies for the intramolecular electron transfers were calculated. A dramatic change in these values was disclosed when comparing both mixed- valent species, which can be explained on the basis of the influence exerted by the 'innocent' co-ligands (polypyridines or cyanides) bonded to the ruthenium centers. This tuning is an important factor in devising molecular devices for energy conversion. © 2002 Elsevier Science Ltd. All rights reserved. |
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