Electron mediation through the thiocyanate bridge: mono- and dinuclear ruthenium diimine complexes and their mixed-valence properties

1988 ◽  
Vol 110 (19) ◽  
pp. 6403-6410 ◽  
Author(s):  
Vaithianathan. Palaniappan ◽  
Sokki. Sathaiah ◽  
Hari Dutt. Bist ◽  
Umesh Chandra. Agarwala
Keyword(s):  
Mixed Valence ◽  
Dinuclear Ruthenium ◽  
Diimine Complexes ◽  
Ruthenium Diimine Complexes

Intervalence transfer in a new benzotriazolate bridged ruthenium-iron complex

2001 ◽  
Vol 79 (2) ◽  
pp. 145-156
Author(s):  
Reginaldo C Rocha ◽  
Henrique E Toma
Keyword(s):  
Near Infrared ◽  
Mixed Valence ◽  
Differential Pulse ◽  
Iron Complex ◽  
Electronic Coupling ◽  
Near Ir ◽  
Metal Metal ◽  
Dinuclear Ruthenium ◽  
Pulse Voltammetry ◽  
Transfer Properties

The unsymmetrical dinuclear ruthenium–iron complexes [(NH3)5Ru–bta–Fe(CN)5]n (where bta = benzotriazolate; n = –2, –1, 0) were prepared as solid sodium salts from [RuII(NH3)5(bta)]+ or [RuIII(NH3)5(bta)]2+ and [FeII(CN)5(H2O)]3– and characterized in aqueous solution by means of electrochemical and spectroelectrochemical methods. UV-vis, near-infrared, IR, and cyclic and differential pulse voltammetry data suggest that the related mixed valent species belong to a valence trapped formulation, featuring localized Ru(III) and Fe(II) oxidation states. In spite of the class II categorization in the Robin and Day scheme, this system shows a remarkable metal–metal electronic coupling, as deduced from an intense, low-energy, and very broad intervalence band in the near-IR region. In addition, the mixed valence state displays enhanced stabilization in relation to the isovalent state. The intervalence transfer properties are discussed on the basis of Hush's theory.Key words: ammineruthenium complexes, cyanoiron complexes, mixed valence, intervalence, benzotriazole, benzotriazolate.

Tuning of Metal–Metal Interactions in Mixed-Valence States of Cyclometalated Dinuclear Ruthenium and Osmium Complexes Bearing Tetrapyridylpyrazine or -benzene

2014 ◽  
Vol 33 (18) ◽  
pp. 4893-4904 ◽  
Author(s):  
Takumi Nagashima ◽  
Takuya Nakabayashi ◽  
Takashi Suzuki ◽  
Katsuhiko Kanaizuka ◽  
Hiroaki Ozawa ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Metal Interactions ◽  
Valence States ◽  
Metal Metal ◽  
Dinuclear Ruthenium ◽  
Osmium Complexes

Driving the Localized-to-Delocalized Transition in Unsymmetrical Dinuclear Ruthenium Mixed-Valence Complexes

2005 ◽  
Vol 58 (11) ◽  
pp. 767 ◽  
Author(s):  
Deanna M. D'Alessandro ◽  
F. Richard Keene
Keyword(s):  
Electronic State ◽  
Ground State ◽  
Mixed Valence ◽  
Electronic Coupling ◽  
Classical Analysis ◽  
Bridging Ligand ◽  
Dinuclear Ruthenium ◽  
State Analysis

The degree of delocalization in the symmetrical complexes [{Ru(bpy)2}2(μ-dpb′)]5+ and [{Ru(bpy)2}2(μ-dpb)]5+ (dpb = 2,3-bis(2-pyridyl)-1,4-benzoquinoxaline; dpb′ = dipyrido(2,3-a;3′,2′-c)benzophenazine; bpy = 2,2′-bipyridine) is diminished by the substitution of the terminal bpy ligands at one end of the complex. The results of a classical analysis for the diastereoisomeric forms of the series of complexes [{Ru(bpy)2}(μ-BL){Ru(pp)2}]5+ (pp = bpy, Me2bpy (4,4′-dimethyl-2,2′-bipyridine), Me4bpy (4,4′,5,5′-tetramethyl-2,2′-bipyridine)) indicate that a greater degree of ground-state delocalization exists in the complexes incorporating the bridging ligand dpb′ compared with the dpb analogue. A two-state analysis in which ΔE 0 (the redox asymmetry) is varied at constant H ab (the electronic coupling) and λ (the reorganizational energy) does not adequately describe the properties of the systems due to the importance of a third electronic state corresponding to the bridging ligand.

scholarly journals Luminescence Quenching and Enhancement by Adsorbed Metal Ions with Ruthenium Diimine Complexes Immobilized on Silica Polyamine Composites

2016 ◽  
Vol 364 (1) ◽  
pp. 47-55
Author(s):  
Edward Rosenberg ◽  
Geoffrey Abbott ◽  
J. B. Alexander Ross ◽  
Riley McVay ◽  
Michelle Terwilliger
Keyword(s):  
Metal Ions ◽  
Luminescence Quenching ◽  
Silica Polyamine Composites ◽  
Diimine Complexes ◽  
Ruthenium Diimine Complexes
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