Heterometallic cyanide-bridged complexes containing RhIRuIIRhI triad: NMR data on exchange reactions and ligand effect transmission

Varshavsky, Yu.S.; Cherkasova, T. G.; Galding, M.R.; Khrustalev, Victor N.; Podkorytov, Ivan S.; Gindin, V. A.; Смирнов, С. Н.; Nikol'skii, A. B.

doi:10.1016/j.jorganchem.2009.04.028

Cited by 10 publications

(1 citation statement)

References 28 publications

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“…For example, multinuclear homometallic ruthenium(II/III) complexes in their mixed-valence (MV) form exhibit a broad intervalence charge-transfer (IVCT) absorption in the near-infrared (NIR) region, which reflects the electronic interactions between both metal centers . Furthermore, related heterometallic ruthenium(II/III) complexes containing Os II/III , , Rh I/III , , Fe II , Cr III , , or Ln III centers were discussed in the same context of metal coupling. On the other hand, there are a limited number of cyanide-bridged iridium(III) complexes containing Ln III , Re I , or Ir III centers.…”

Section: Introductionmentioning

confidence: 99%

Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes

et al. 2016

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We report a series of cyanide-bridged, heterodinuclear iridium(III)-ruthenium(II) complexes with the generalized formula [Ir((R2)2-ppy)2(CN)(μ-CN)Ru(bpy)(tpy-R1)]PF6 (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine, and tpy = 2,2':6',2″-terpyridine). The structural, spectroscopic, and electrochemical properties were analyzed in the context of variation of the electron-withdrawing (e.g., -F, -Br, -CHO) and -donating (e.g., -Me) and extended π-conjugated groups at several positions. In total, ten dinuclear complexes and the appropriate model complexes have been prepared. The iridium(III)-based emission is almost fully quenched in these complexes, and only the ruthenium(II)-based emission is observed, which indicates an efficient energy transfer toward the Ru center. Upon oxidation of the Ru center, the fluorinated complexes 2 exhibit a broad intervalence charge-transfer transition in the near-infrared region. The complexes are assigned to a weakly coupled class II system according to the Robin-Day classification. The electronic structure was evaluated by density functional theory (DFT) and time-dependent DFT calculations to corroborate the experimental data.

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Section: Introductionmentioning

confidence: 99%

Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes

et al. 2016

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Synthesis of Trinuclear Heterobimetallic Cyanido‐Bridged Complexes from the Reaction of [Mn^I(CN)(CO)(tBuNC)₄] with Transition‐Metal Chlorides

et al. 2014

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The reaction of [Mn(CN)(CO)(tBuNC)4] with MnCl2·4H2O, FeCl3·9H2O, NiCl2·6H2O, and CuCl2·2H2O, respectively, led to the formation of trinuclear heterobimetallic complexes that comprised two manganese moieties, with each coordinating the corresponding metal chloride entities through cyanide bridges. The mixed‐valence trinuclear MnI–CN–MnII–NC–MnI complex as well as the MnI–CN–NiII–NC–MnI derivative have been characterized by X‐ray structure analyses. In the case of the copper and iron compounds that exhibit easily reducable central metal ions, intramolecular electron transfer from manganese(I) to copper(II) or iron(III), respectively, is shown by the presence of metal‐to‐metal charge‐transfer (MMCT) bands as well as by EPR spectroscopy. Moreover, the iron complex shows a subsequent disproportionation, which was demonstrated by the isolation and crystallographic characterization of the reduced species with two manganese(I) complex units coordinating one FeIICl2 moiety.

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Interfragment transmission of electronic effects of π-acceptor ligands in heterometallic triad complexes with trans-[Ru(Py)4(CN)2] as a central unit

et al. 2012

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Heterometallic cyanide-bridged complexes containing RhIRuIIRhI triad: NMR data on exchange reactions and ligand effect transmission

Cited by 10 publications

References 28 publications

Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes

Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes

Synthesis of Trinuclear Heterobimetallic Cyanido‐Bridged Complexes from the Reaction of [Mn^I(CN)(CO)(tBuNC)₄] with Transition‐Metal Chlorides

Interfragment transmission of electronic effects of π-acceptor ligands in heterometallic triad complexes with trans-[Ru(Py)4(CN)2] as a central unit

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Heterometallic cyanide-bridged complexes containing RhIRuIIRhI triad: NMR data on exchange reactions and ligand effect transmission

Cited by 10 publications

References 28 publications

Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes

Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes

Synthesis of Trinuclear Heterobimetallic Cyanido‐Bridged Complexes from the Reaction of [MnI(CN)(CO)(tBuNC)4] with Transition‐Metal Chlorides

Interfragment transmission of electronic effects of π-acceptor ligands in heterometallic triad complexes with trans-[Ru(Py)4(CN)2] as a central unit

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Synthesis of Trinuclear Heterobimetallic Cyanido‐Bridged Complexes from the Reaction of [Mn^I(CN)(CO)(tBuNC)₄] with Transition‐Metal Chlorides