The Creutz-Taube complex revisited

Fuerholz, Urs; Buergi, H. B.; Wagner, F. E.; Stebler, A.; Ammeter, J. H.; Krausz, Elmars; Clark, Robin J. H.; Stead, M.; Lüdi, A.

doi:10.1021/ja00313a025

Cited by 105 publications

(75 citation statements)

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“…Therefore, the two combinations of the orbitals bearing the unpaired electron cannot have large contributions towards the bridging ligand and we expect a small energy splitting between the in-phase and out-of-phase combinations of such d orbitals and, consequently, a small exchange coupling constant for this complex. Experimentally, the authors proposed a maximum negative value for the coupling constant of Ϫ6 cm Ϫ1 from magnetic susceptibility measurements, [42] in very good agreement with the presently calculated value at the B3LYP level of Ϫ2.6 cm Ϫ1 . Figure 2.…”

Section: Results Of the Full Structuressupporting

confidence: 79%

Exchange Coupling in Metal Complexes of the Second Transition Series: A Theoretical Exploration

2003

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Section: Results Of the Full Structuressupporting

confidence: 79%

Exchange Coupling in Metal Complexes of the Second Transition Series: A Theoretical Exploration

2003

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“…Although interpretation of the Creutz-Taube ion, [(NH 3 ) 5 Ru(pz)Ru(NH 3 ) 5 ] 5C , has remained controversial, its properties are analogous to those of [(Cl) 3 Ru(tppz)Ru(Cl) 3 ] K and it is also in class II-III (Fürholz et al 1984;Demadis et al 2001). Coordination geometries are asymmetrical.…”

Section: It Icmentioning

confidence: 99%

“…It is delocalized in (3) which is in class III and it is 'intermediate' in (2). Both limiting descriptions have been suggested to apply depending on the observation made or the assumptions used in a theoretical analysis (Fürholz et al 1984;Demadis et al 2001).…”

Section: Introductionmentioning

confidence: 99%

Probing the localized-to-delocalized transition

Concepcion

Dattelbaum

Meyer

et al. 2007

Phil. Trans. R. Soc. A.

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Detailed understanding of the transition between localized and delocalized behaviour in mixed valence compounds has been elusive as evidenced by many interpretations of the Creutz-Taube ion, [(NH 3 ) 5 Ru(pz)Ru(NH 3 ) 5 ] 5C . In a review in 2001, experimental protocols and a systematic model to probe this region were proposed and applied to examples in the literature. The model included: (i) multiple orbital interactions in ligand-bridged transition metal complexes, (ii) inclusion of spin-orbit coupling which, for dp 5 -dp 6 complexes, leads to five low-energy bands, two from interconfigurational (dp/dp) transitions at the dp 5 site and three from intervalence transfer transitions, (iii) differences in time scale between coupled vibrations and solvent modes which can result in solvent averaging with continued electronic asymmetry defining 'class II-III', an addition to the Robin-Day classification scheme, and (iv) delineation of coupled vibrations into barrier vibrations and 'spectator' vibrations. The latter provide direct insight into localization or delocalization and time scales for electron transfer. In this paper, the earlier model is applied to a series of mixed-valence molecules.

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“…These bands are assigned 7,27,[39][40][41][42] to skeletal vibrational modes involving stretching vibrations of Ru-N of the different ligands and bending (N-Ru-N) of the NH 3 .…”

Section: Resultsmentioning

confidence: 99%

“…[4][5][6][7][8][9][10][11][12][13] In addition, mixed-valence complexes have attracted a lot of attention due to the interest in the synthesis of the so-called molecular wires. These materials can be defined as "a molecule between two reservoirs of electrons" or "a molecule that conducts electrical current between two electrodes", according to Kirczenow 14 and Ratner, 15 respectively.…”

Section: Introductionmentioning

confidence: 99%

Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

Pinheiro¹,

Paulo²,

Abreu³

et al. 2012

Dalton Trans.

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Complexes of the type {[( pyS)Ru(NH 3 ) 4 ] 2 -μ-L}n , where pyS = 4-mercaptopyridine, L = 4,4′-dithiodipyridine ( pySSpy), pyrazine ( pz) and 1,4-dicyanobenzene (DCB), and n = +4 and +5 for fully reduced and mixed-valence complexes, respectively, were synthesized and characterized. Electrochemical data showed that there is electron communication between the metal centers with comproportionation constants of 33.2, 1.30 × 10 8 and 5.56 × 10 5 for L = pySSpy, pz and DCB, respectively. It was also observed that the electronic coupling between the metal centers is affected by the π-back-bonding interaction toward the pyS ligand. Raman spectroscopy showed a dependence of the intensity of the vibrational modes on the exciting radiations giving support to the assignments of the electronic transitions. The degree of electron communication between the metal centers through the bridging ligands suggests that these systems can be molecular wire materials.

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The Creutz-Taube complex revisited

Cited by 105 publications

References 0 publications

Exchange Coupling in Metal Complexes of the Second Transition Series: A Theoretical Exploration

Exchange Coupling in Metal Complexes of the Second Transition Series: A Theoretical Exploration

Probing the localized-to-delocalized transition

Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

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