Unusual phenomenon in the chemistry of orthometalated ruthenium (II) complexes

Ryabov, Alexander D.; Estevez, Hebert; Alexandrova, Larissa; Pfeffer, Michel; Lagadec, Ronan Le

doi:10.1016/j.ica.2005.05.034

Cited by 20 publications

(19 citation statements)

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“…The large similarity of the X-ray data of both isomers of this complex (denoted as yellow and orange) has been established before [ 24 ]. However, a more careful examination of the bond lengths in the interactions between N atom and C atom in the nitrile ligands shows discrepancies in the corresponding values ( Figure 2 ).…”

Section: Resultssupporting

confidence: 69%

“…The extinction coefficient of longer wavelength absorption of the orange compound was slightly (about 5–13% depending on the solvent) higher than that of the yellow sample. Interestingly that this difference in MeCN solution spectra was less than in the spectra run in other solutions such as CH 2 Cl 2 and MeOH [ 24 ].…”

Section: Resultsmentioning

confidence: 99%

“…The yellow and orange forms of the ruthenium complex, [Ru( o -C 6 H 4 -py)(MeCN) 4 ] + , were synthesized as described in reference [ 24 ]. Their UV-Vis spectra were obtained in freshly prepared MeCN solutions using a Varian Cary 400 UV-Vis spectrophotometer.…”

Section: Methodsmentioning

confidence: 99%

“…The new orange compound turned out to be slightly more stable than the yellow one and additionally a small difference between them was also observed by UV-Vis spectroscopy. In the first communication on the subject the presence of two structures was suggested [ 24 ], but an explanation for this strange phenomenon was not provided since more studies were deemed necessary. Detailed analysis of the X-ray data revealed slight difference in the several bond lengths between the yellow and orange compounds.…”

Section: Introductionmentioning

confidence: 99%

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Hybridization vs. Bond Stretching Isomerism in Ru(II) Cyclometalated Complexes of 2-Phenylpyridine

et al. 2011

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The phenomenon of formation of two isomers, yellow and orange, of the cyclometalated Ru(II) complex, [Ru(o-C6H4-py)(MeCN)4]+, was investigated by EELS spectroscopy and theoretical calculations. Both forms show very similar structures and spectroscopic properties, but slight differences in X-ray data and absorption between them were noted. No double minimum on the potential energy surface was found and thus these two forms cannot be considered as bond stretching isomers. However, the DFT study revealed the change in the hybridization of the carbon in trans-position of one of acetonitrile ligands. This effect can be responsible for the difference in colour. The results of the theoretical modelling coincide well with the experimental EELS data.

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Section: Resultssupporting

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hybridization vs. Bond Stretching Isomerism in Ru(II) Cyclometalated Complexes of 2-Phenylpyridine

et al. 2011

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“…Ligands bearing electron-withdrawing groups on the phenyl ring were found to react faster than those with electron-donating moieties due to the increased acidity of the aryl proton that undergoes the requisite C-H bond-breaking event. As documented by Ryabov et al, 72 electron-rich precursors can turn green after brief exposure to air, but no detectable change in the structure via NMR spectroscopy was observed and the target dyes could still be isolated in decent yields. 72 Both solvated intermediates were suitable for subsequent ligation by two dcbpy ligands in an aqueous methanolic mixture; four equivalents of base were required to solubilize the anchoring ligands and water was not used in the synthesis of certain intermediates to overcome solubility issues (e.g., [Ru(p-cymene)(MeCN) 2 …”

Section: Ru Dyes Bearing a Bidentate Cyclometalating Ligand 41 Synthmentioning

confidence: 71%

Cycloruthenated sensitizers: improving the dye-sensitized solar cell with classical inorganic chemistry principles

2012

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A divergence from the conventional approach to chromophore design has led to the establishment of many exciting new benchmarks for the dye-sensitized solar cell (DSSC), including the first documented power conversion efficiency in excess of 12% at 1 sun illumination [Yella et al., Science 2011, 334, 629]. Paramount to these advances is the deviation from polypyridyl ruthenium dyes bearing NCS(-) ligands, such as [Ru(dcbpy)(2)(NCS)(2)] (N3; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine). While metal-free and porphyrin dyes have demonstrated much promise, the discovery that the NCS(-) ligands of N3 can be replaced by anionic, chelating cyclometalating ligands without compromising device efficiencies has ushered in a new era of ruthenium dye development. A particularly appealing feature of this class of dyestuff is that they offer acute control of the frontier molecular orbitals to enable the precise attenuation of both the ground and excited state redox potentials through judicious chemical modification of the aryl ring. This Perspective summarizes very recent developments in the field, and demonstrates how the new and rapidly expanding class of Ru-based sensitizers provides a conduit for enhancing the performance (and potentially the stability) of the DSSC.

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Photoinduzierte Rutheniumkatalysierte C‐H‐Arylierungen bei Umgebungstemperatur

et al. 2020

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Rutheniumkatalysierte C‐H‐Arylierungen wurden bei Umgebungstemperatur durch sichtbares Licht ohne zusätzlichen Photokatalysator ermöglicht. Die Robustheit dieser rutheniumkatalysierten C‐H‐Funktionalisierung wurde in einer breiten Auswahl von sensitiven funktionellen Gruppen und synthetisch nützlichen Pyrazolen, Triazolen und empfindlichen Nucleosiden und Nucleotiden sowie durch mehrfache C‐H‐Funktionalisierungen verdeutlicht. Biscyclometallierte Rutheniumkomplexe wurden als Schlüsselintermeditate in der Photoredox‐Rutheniumkatalyse durch detaillierte rechnerische und experimentelle mechanistische Studien identifiziert. Berechnungen deuten darauf hin, dass eine in situ gebildete, photoaktive Rutheniumspezies vorzugsweise einen Inner‐Sphere‐Elektronentransfer durchläuft.

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Unusual phenomenon in the chemistry of orthometalated ruthenium (II) complexes

Cited by 20 publications

References 4 publications

Hybridization vs. Bond Stretching Isomerism in Ru(II) Cyclometalated Complexes of 2-Phenylpyridine

Hybridization vs. Bond Stretching Isomerism in Ru(II) Cyclometalated Complexes of 2-Phenylpyridine

Cycloruthenated sensitizers: improving the dye-sensitized solar cell with classical inorganic chemistry principles

Photoinduzierte Rutheniumkatalysierte C‐H‐Arylierungen bei Umgebungstemperatur

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