Highly coupled mixed-valence dinuclear ruthenium and osmium complexes with a bis-cyclometalating terpyridine analog as bridging ligand

1993 ◽  
Vol 32 (21) ◽  
pp. 4539-4543 ◽  
Author(s):  
Marc Beley ◽  
Jean Paul Collin ◽  
Jean Pierre Sauvage
Keyword(s):  
Mixed Valence ◽  
Bridging Ligand ◽  
Dinuclear Ruthenium ◽  
Osmium Complexes

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.

Mixed-valence properties of a dinuclear ruthenium complex bridged by bis(phenylcyanamido)tetrazine

2014 ◽  
Vol 92 (11) ◽  
pp. 1081-1085 ◽  
Author(s):  
Fatemeh Habibagahi ◽  
Robert J. Crutchley
Keyword(s):  
Ruthenium Complex ◽  
Mixed Valence ◽  
Transition Dipole Moment ◽  
The Novel ◽  
Transition Dipole ◽  
H Nmr ◽  
Bridging Ligand ◽  
Metal Metal ◽  
Dinuclear Ruthenium ◽  
The Stability

The novel bridging ligand 3,6-bis(phenylcyanamido)-1,2,4,5-tetrazine (tdpcH2) and its dinuclear complex [{Ru(ttpy)(bpy)}2(μ-tdpc)][PF6]2 were prepared and characterized by elemental analysis and 1H NMR spectroscopy. Cyclic voltammetry and vis-NIR and IR spectroelectrochemistry of [{Ru(ttpy)(bpy)}2(μ-tdpc)]2+ showed that [{Ru(ttpy)(bpy)}2(μ-tdpc)]3+ is a Class II mixed-valence system with metal−metal coupling of 400 cm−1 assuming a transition dipole moment length of 21 Å. DFT calculations of tdpc2− suggested that the stability of the HOMO results in weak metal−metal coupling via the hole-superexchange mechanism.

Revisiting Dinuclear Ruthenium Water Oxidation Catalysts: Effect of Bridging Ligand Architecture on Catalytic Activity

2021 ◽  
Vol 60 (3) ◽  
pp. 1806-1813
Author(s):  
Husain N. Kagalwala ◽  
Mahesh S. Deshmukh ◽  
Elamparuthi Ramasamy ◽  
Neelima Nair ◽  
Rongwei Zhou ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Water Oxidation ◽  
Oxidation Catalysts ◽  
Bridging Ligand ◽  
Dinuclear Ruthenium

Bridging ligand planarity as a route to long-lived, near infrared emitting dinuclear ruthenium(ii) complexes

2006 ◽  
pp. 1301 ◽  
Author(s):  
Matthew I. J. Polson ◽  
Frédérique Loiseau ◽  
Sebastiano Campagna ◽  
Garry S. Hanan
Keyword(s):  
Near Infrared ◽  
Bridging Ligand ◽  
Dinuclear Ruthenium

Modulation of Internuclear Communication in Multinuclear Ruthenium(II) Polypyridyl Complexes

2003 ◽  
Vol 68 (8) ◽  
pp. 1467-1487 ◽  
Author(s):  
Wesley R. Browne ◽  
Frances Weldon ◽  
Adrian Guckian ◽  
Johannes G. Vos
Keyword(s):  
Ground State ◽  
Weak Interactions ◽  
Electrochemical Studies ◽  
Protonation State ◽  
Ruthenium Polypyridyl ◽  
Bridging Ligands ◽  
Polypyridyl Complexes ◽  
Bridging Ligand ◽  
Dinuclear Ruthenium ◽  
Ruthenium Polypyridyl Complexes

The syntheses and characterisation of a series of mononuclear and dinuclear ruthenium polypyridyl complexes based on the bridging ligands 1,3-bis-[5-(2-pyridyl)-1H-1,2,4-triazol-3-yl]benzene, 1,4-bis-[5-(2-pyridyl)-1H-1,2,4-triazol-3-yl]benzene, 2,5-bis-[5-(2-pyridyl)-1H-1,2,4-triazol-3-yl]thiophene, 2,5-bis-[5-pyrazinyl-1H-1,2,4-triazol-3-yl]thiophene are reported. Electrochemical studies indicate that in these systems, the ground state interaction is critically dependent on the nature of the bridging ligand and its protonation state, with strong and weak interactions being observed for thiophene- and phenylene-bridged complexes, respectively.

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
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