Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes

We report here the spectroscopic properties of four very closely related mixed-valence cyanide-bridged bimetallic complexes, trans-[Ru(T)(bpy)(μ-NC) Ru(L)4(CN)]3+ (T = tris(1-pyrazolyl)methane (tpm, a) or 2,2′;6′,2″-terpyridine, (tpy, b), and L = pyridine (py, 1) or 4-methoxypyridine (MeOpy, 2)). In...

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Detalles Bibliográficos
Autores principales: Cadranel, Alejandro, Baraldo Victorica, Luis Mario
Publicado: 2014
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v53_n16_p8221_Pieslinger
http://hdl.handle.net/20.500.12110/paper_00201669_v53_n16_p8221_Pieslinger
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_00201669_v53_n16_p8221_Pieslinger
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spelling paper:paper_00201669_v53_n16_p8221_Pieslinger2023-06-08T14:40:42Z Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes Cadranel, Alejandro Baraldo Victorica, Luis Mario We report here the spectroscopic properties of four very closely related mixed-valence cyanide-bridged bimetallic complexes, trans-[Ru(T)(bpy)(μ-NC) Ru(L)4(CN)]3+ (T = tris(1-pyrazolyl)methane (tpm, a) or 2,2′;6′,2″-terpyridine, (tpy, b), and L = pyridine (py, 1) or 4-methoxypyridine (MeOpy, 2)). In acetonitrile all the complexes present intervalence charge transfer (IVCT) transitions in the NIR region, but their intensities are widely different, with the intensity of the transition observed for 1a-b3+ around four times larger than that observed for 2a-b 3+. This contrasting behavior can be traced to the different nature of the dπ acceptor orbitals involved in these transitions, as confirmed by (TD)DFT calculations. The spectroscopy of 1a-b3+ provides evidence that the spin density is delocalized over the two ruthenium ions, such as a narrowing of the IVCT bands that results in the resolution of the expected three bands, and a weak solvent dependence of the energy of these transitions. The spectroscopy of 2a-b3+ instead indicates that the spin density is localized on one ruthenium ion. The IVCT in these systems is particularly weak due to the configuration of the Ru(III), where the vacant orbital is perpendicular to the cyanide bridge. © 2014 American Chemical Society. Fil:Cadranel, A. 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. 2014 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v53_n16_p8221_Pieslinger http://hdl.handle.net/20.500.12110/paper_00201669_v53_n16_p8221_Pieslinger
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description We report here the spectroscopic properties of four very closely related mixed-valence cyanide-bridged bimetallic complexes, trans-[Ru(T)(bpy)(μ-NC) Ru(L)4(CN)]3+ (T = tris(1-pyrazolyl)methane (tpm, a) or 2,2′;6′,2″-terpyridine, (tpy, b), and L = pyridine (py, 1) or 4-methoxypyridine (MeOpy, 2)). In acetonitrile all the complexes present intervalence charge transfer (IVCT) transitions in the NIR region, but their intensities are widely different, with the intensity of the transition observed for 1a-b3+ around four times larger than that observed for 2a-b 3+. This contrasting behavior can be traced to the different nature of the dπ acceptor orbitals involved in these transitions, as confirmed by (TD)DFT calculations. The spectroscopy of 1a-b3+ provides evidence that the spin density is delocalized over the two ruthenium ions, such as a narrowing of the IVCT bands that results in the resolution of the expected three bands, and a weak solvent dependence of the energy of these transitions. The spectroscopy of 2a-b3+ instead indicates that the spin density is localized on one ruthenium ion. The IVCT in these systems is particularly weak due to the configuration of the Ru(III), where the vacant orbital is perpendicular to the cyanide bridge. © 2014 American Chemical Society.
author Cadranel, Alejandro
Baraldo Victorica, Luis Mario
spellingShingle Cadranel, Alejandro
Baraldo Victorica, Luis Mario
Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes
author_facet Cadranel, Alejandro
Baraldo Victorica, Luis Mario
author_sort Cadranel, Alejandro
title Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes
title_short Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes
title_full Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes
title_fullStr Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes
title_full_unstemmed Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes
title_sort influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes
publishDate 2014
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v53_n16_p8221_Pieslinger
http://hdl.handle.net/20.500.12110/paper_00201669_v53_n16_p8221_Pieslinger
work_keys_str_mv AT cadranelalejandro influenceoftheelectronicconfigurationinthepropertiesofd6d5mixedvalencecomplexes
AT baraldovictoricaluismario influenceoftheelectronicconfigurationinthepropertiesofd6d5mixedvalencecomplexes
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