Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers
We report here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4Ru II(μ-NC)FeIII(CN)5]- (with L = pyridine or 4-dimethylaminopyridine (dmap) and L′ = pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be...
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todo:paper_00201693_v374_n1_p334_Rossi2023-10-03T14:17:21Z Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers Rossi, M.B. Alborés, P. Baraldo, L.M. Cyanide bridged complexes Intervalence charge transfer Metal-metal interaction Mixed valence complexes Solvent effect Spectroelectrochemistry We report here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4Ru II(μ-NC)FeIII(CN)5]- (with L = pyridine or 4-dimethylaminopyridine (dmap) and L′ = pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be adjusted smoothly by changing the acceptor properties of the solvent and the σ donor properties of the L′ pyridine ligand. In solution these complexes exhibit an intense solvent-dependent MM′CT (RuII → FeIII) absorption in the near infrared region. Analysis of this band in different complexes and solvents suggests an enhanced interaction as the energies of the metal centers come closer. From this trend the anion trans-[(dmap)5Ru(μ-NC)Fe(CN)5]- (dmap = 4-dimethylaminopyridine) in water is expected to belong to the class II-III, but its spectral properties indicates a ground state with Ru(III)-Fe(II) character. The stabilization of this electronic isomer is probably related to the better donor properties of the hexacyanoferrate(II) moiety and its stronger interaction with water. © 2011 Elsevier B.V. All rights reserved. Fil:Rossi, M.B. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Alborés, P. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Baraldo, L.M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00201693_v374_n1_p334_Rossi |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Cyanide bridged complexes Intervalence charge transfer Metal-metal interaction Mixed valence complexes Solvent effect Spectroelectrochemistry |
| spellingShingle |
Cyanide bridged complexes Intervalence charge transfer Metal-metal interaction Mixed valence complexes Solvent effect Spectroelectrochemistry Rossi, M.B. Alborés, P. Baraldo, L.M. Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers |
| topic_facet |
Cyanide bridged complexes Intervalence charge transfer Metal-metal interaction Mixed valence complexes Solvent effect Spectroelectrochemistry |
| description |
We report here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4Ru II(μ-NC)FeIII(CN)5]- (with L = pyridine or 4-dimethylaminopyridine (dmap) and L′ = pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be adjusted smoothly by changing the acceptor properties of the solvent and the σ donor properties of the L′ pyridine ligand. In solution these complexes exhibit an intense solvent-dependent MM′CT (RuII → FeIII) absorption in the near infrared region. Analysis of this band in different complexes and solvents suggests an enhanced interaction as the energies of the metal centers come closer. From this trend the anion trans-[(dmap)5Ru(μ-NC)Fe(CN)5]- (dmap = 4-dimethylaminopyridine) in water is expected to belong to the class II-III, but its spectral properties indicates a ground state with Ru(III)-Fe(II) character. The stabilization of this electronic isomer is probably related to the better donor properties of the hexacyanoferrate(II) moiety and its stronger interaction with water. © 2011 Elsevier B.V. All rights reserved. |
| format |
JOUR |
| author |
Rossi, M.B. Alborés, P. Baraldo, L.M. |
| author_facet |
Rossi, M.B. Alborés, P. Baraldo, L.M. |
| author_sort |
Rossi, M.B. |
| title |
Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers |
| title_short |
Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers |
| title_full |
Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers |
| title_fullStr |
Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers |
| title_full_unstemmed |
Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers |
| title_sort |
exploring the properties of mixed valence cyanide bridged dinuclear complexes: solvent stabilization of electronic isomers |
| url |
http://hdl.handle.net/20.500.12110/paper_00201693_v374_n1_p334_Rossi |
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1807323225440387072 |