Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Parthey, Matthias; Gluyas, Josef B. G.; Fox, Mark A.; Low, Paul J.; Kaupp, Martin

doi:10.1002/chem.201304947

Cited by 84 publications

(118 citation statements)

References 65 publications

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“…[43] However,t he NIR bands of the MV species 4c + + and 4d + + could not be observed by chemical or electrochemicalm ethods, whichm ay be due to the high instability or smaller change of the torsion angle from their neutralt oM V state in solution at room temperature. [70,71] …”

Section: Uv/vis/nir Spectroscopymentioning

confidence: 98%

Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

Kong

Xue

Jang

et al. 2015

Chemistry A European J

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The synthesis and characterization of a series of biphenyl-derived binuclear ruthenium complexes with terminal {RuCl(CO)(PMe3)3} moieties and different structural arrangements of the phenyl rings are reported. Electrochemical studies revealed that the two metal centers of the binuclear ruthenium complexes interact with each other through the biphenyl bridge, and the redox splittings ΔE1/2 show a strong linear correlation with cos(2) ϕ, where ϕ is the torsion angle between the two phenyl rings. A combination of electrochemical, UV/Vis/NIR, and in situ IR differential spectroelectrochemical analysis clearly showed that: 1) the intramolecular electronic couplings in the binuclear ruthenium complexes could be modulated by changing ϕ; 2) the electronic ground state of the mixed-valent cations changes from delocalized to localized through the biphenyl bridge with increasing torsion angle ϕ, that is, the redox processes of these complexes change from significant involvement of the bridging ligand to an oxidation behavior with less participation of the bridge.

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Section: Uv/vis/nir Spectroscopymentioning

confidence: 98%

Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

Kong

Xue

Jang

et al. 2015

Chemistry A European J

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“…We became interested in elucidating the dependence on acyclic versus cyclic bridging units in more detail by cyclic voltammetry and EPR/UV–vis–NIR spectroelectrochemistry. With regard to conformational flexibility and the lack of it, it deserves mentioning that Low and co-workers [11–12] have shown how rotamers can indeed influence the electronic coupling in bis-ruthenium complexes separated by oligoynediyl spacers. In addition, an increased interaction between redox centres upon linking them together in cyclic structures was previously observed in ferrocene-dimers [13].…”

Section: Introductionmentioning

confidence: 99%

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

Jiang¹,

Mazzanti

Parker³

et al. 2015

Beilstein J. Org. Chem.

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SummaryA selection of cyclic and acyclic acetylenic scaffolds bearing two tetrathiafulvalene (TTF) units was prepared by different metal-catalyzed coupling reactions. The bridge separating the two TTF units was systematically changed from linearly conjugated ethyne, butadiyne and tetraethynylethene (trans-substituted) units to a cross-conjugated tetraethynylethene unit, placed in either acyclic or cyclic arrangements. The cyclic structures correspond to so-called radiaannulenes having both endo- and exocyclic double bonds. Interactions between two redox-active TTF units in these molecules were investigated by cyclic voltammetry, UV–vis–NIR and EPR absorption spectroscopical methods of the electrochemically generated oxidized species. The electron-accepting properties of the acetylenic cores were also investigated electrochemically.

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“…Elemental analyses were performed at the Center for Advanced Materials Analysis, Technical Department, Tokyo Institute of Technology. The di-ethynylated furan [15], pyrrole [16], and DPE [13] and the metal precursors [Cp ⁄ Fe(dppe)Cl] [17] were prepared by following the published procedures. Other chemicals were purchased and used as received.…”

Section: General Methodsmentioning

confidence: 99%

Synthesis and properties of diiron complexes with heteroaromatic linkers: An approach for modulation of organometallic molecular wire

Tanaka¹,

Ishisaka²,

Koike³

et al. 2015

Polyhedron

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Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Cited by 84 publications

References 65 publications

Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

Synthesis and properties of diiron complexes with heteroaromatic linkers: An approach for modulation of organometallic molecular wire

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