Busca avançada
Ano de início
Entree


Electrostatic bending and outer-sphere intervalence transfer in a flexible ligand-bridged ruthenium(III)-iron(II) complex

Texto completo
Autor(es):
Aguirre-Araque, Juan S. ; Rocha, Reginaldo C. ; Toma, Henrique E.
Número total de Autores: 3
Tipo de documento: Artigo Científico
Fonte: Journal of Coordination Chemistry; v. 71, n. 11-13, p. 13-pg., 2018-01-01.
Resumo

In the mixed-valence complex [Ru-III(NH3)(5)(-dpypn)Fe-II(CN)(5)] with the flexible bridging ligand 1,3-di(4-pyridyl)propane (dpypn), electrostatic interactions between the {Ru(NH3)(5)}(3+) and {Fe(CN)(5)}(3-) moieties drive a strong bending of dpypn and approximation of the Ru-III and Fe-II centers, from which the enhanced electronic coupling between metal ions produces an intense intervalence-transfer absorption in the near-infrared region. Density functional theory calculations corroborate both the electrostatic bending in this heterobinuclear complex and a linear geometry in the homobinuclear counterparts [Ru(NH3)(5)(-dpypn)Ru(NH3)(5)](5+) and [Fe(CN)(5)(-dpypn)Fe(CN)(5)](5-), for which no evidence of electronic coupling was found because of the separation between metal centers. Furthermore, the heterobinuclear species formed an inclusion complex with -cyclodextrin where the imposed linear geometry prevents significant electronic coupling and intervalence charge transfer between the Ru-III and Fe-II centers. [GRAPHICS] . (AU)

Processo FAPESP: 13/24725-4 - Química supramolecular e nanotecnologia
Beneficiário:Henrique Eisi Toma
Modalidade de apoio: Auxílio à Pesquisa - Temático