Tuning of the reorganization energies by ‘innocent’ co-ligands in novel mixed-valent dinuclear ruthenium complexes
| Autor: | Monica Mercedes Vergara, Florencia Fagalde, Monica E. Garcia Posse, Néstor E. Katz |
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| Rok vydání: | 2003 |
| Předmět: |
Pyrazine
chemistry.chemical_element Photochemistry Inorganic Chemistry RUTHENIUM COMPLEXES chemistry.chemical_compound Materials Chemistry Physical and Theoretical Chemistry Spectral data chemistry.chemical_classification Aqueous solution Otras Ciencias Químicas Ciencias Químicas INTRAMOLECULAR ELECTRON TRANSFER REORGANIZATION ENERGIES INVERTED REGION Ruthenium Crystallography chemistry Mixed valent Intramolecular force Counterion Absorption (chemistry) MIXED-VALENCE CIENCIAS NATURALES Y EXACTAS ENERGY CONVERSION |
| Zdroj: | Polyhedron. 22:465-471 |
| ISSN: | 0277-5387 |
| DOI: | 10.1016/s0277-5387(02)01368-2 |
| Popis: | 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. Fil: Vergara, Monica Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina Fil: García Posse, Mónica Ema. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina Fil: Fagalde, Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina Fil: Katz, Néstor Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina |
| Databáze: | OpenAIRE |
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