Dinuclear ruthenium bipyridine complexes with a bis(iminodioxolene)-meta-phenylene ligand: magnetic coupling and mixed valence character of the semiquinonato species

2005 ◽  
pp. 3868 ◽  
Author(s):  
Fabrizia Fabrizi De Biani ◽  
Andrea Dei ◽  
Claudio Sangregorio ◽  
Lorenzo Sorace
Keyword(s):  
Mixed Valence ◽  
Magnetic Coupling ◽  
Dinuclear Ruthenium

Electric field controllable magnetic coupling of localized spins mediated by itinerant electrons: a toy model

2017 ◽  
Vol 19 (38) ◽  
pp. 26098-26106 ◽  
Author(s):  
Andrew Palii ◽  
Sergey Aldoshin ◽  
Boris Tsukerblat ◽  
Juan Modesto Clemente-Juan ◽  
Alejandro Gaita-Ariño ◽  
...  
Keyword(s):  
Electric Field ◽  
Mixed Valence ◽  
Magnetic Coupling ◽  
Itinerant Electron ◽  
Itinerant Electrons

In this paper, we propose a toy model to describe the magnetic coupling between the localized spins mediated by the itinerant electron in partially delocalized mixed-valence (MV) systems.

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.

Synthesis of mixed-valence hexanuclear Mn(ii/iii) clusters from its Mn(ii) precursor: variations of catecholase-like activity and magnetic coupling

2015 ◽  
Vol 44 (21) ◽  
pp. 9795-9804 ◽  
Author(s):  
Paramita Kar ◽  
Yumi Ida ◽  
Takuya Kanetomo ◽  
Michael G. B. Drew ◽  
Takayuki Ishida ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Mixed Valence ◽  
Magnetic Coupling ◽  
Magnetic Interactions ◽  
1D Coordination Polymer

A pyrazine bridged 1D coordination polymer of Mn(ii) has been oxidized with n-Bu4NMnO4 to hexanuclear Mn(ii/iii) complexes. Their catecholase-like activities and magnetic interactions have been studied.

Infrared Study of the Class II/Class III Boundary in Mixed-Valence Dinuclear Ruthenium Complexes

2001 ◽  
Vol 123 (7) ◽  
pp. 1396-1402 ◽  
Author(s):  
Maria C. DeRosa ◽  
Christopher A. White ◽  
Christopher E. B. Evans ◽  
Robert J. Crutchley
Keyword(s):  
Mixed Valence ◽  
Ruthenium Complexes ◽  
Class Ii ◽  
Class Iii ◽  
Infrared Study ◽  
Dinuclear Ruthenium ◽  
Dinuclear Ruthenium Complexes
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