About: UV-vis-NIR and EPR characterisation of the redox series [MQ3]2+,+,0,,2, M = Ru or Os, and Q = o-quinone derivative

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About: UV-vis-NIR and EPR characterisation of the redox series [MQ3]2+,+,0,,2, M = Ru or Os, and Q = o-quinone derivative Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	The neutral title compounds with Q = 3,5-di-tert-butyl-o-quinone or 4,6-di-tert-butyl-N-phenyl-o-iminobenzoquinone (Qx) were studied by UV-vis-NIR spectroelectrochemistry and by EPR spectroscopy in the case of the odd-electron monocation and monoanion intermediates. Supported by DFT and TD-DFT calculations, the results indicate stepwise electron removal from predominantly ligand-based delocalised MOs on oxidation whereas the stepwise electron uptake on reduction involves unoccupied MOs with considerably metal–ligand mixed character. In both cases, the strong near-infrared absorption of the neutral precursors diminishes. In comparison to the ruthenium series, the osmium analogues exhibit larger transition energies from enhanced MO splitting and a different EPR response due to the higher spin–orbit coupling. The main difference between the quinone (1n, 2n) and corresponding monoiminoquinone systems (3n, 4n) is the shift of about 0.6 V to lower potentials for the monoimino analogues. While the absorption features do not differ markedly, the EPR data reflect a higher degree of covalent bonding for the complexes with monoimino ligands. The neutral title compounds with Q = 3,5-di-tert-butyl-o-quinone or 4,6-di-tert-butyl-N-phenyl-o-iminobenzoquinone (Qx) were studied by UV-vis-NIR spectroelectrochemistry and by EPR spectroscopy in the case of the odd-electron monocation and monoanion intermediates. Supported by DFT and TD-DFT calculations, the results indicate stepwise electron removal from predominantly ligand-based delocalised MOs on oxidation whereas the stepwise electron uptake on reduction involves unoccupied MOs with considerably metal–ligand mixed character. In both cases, the strong near-infrared absorption of the neutral precursors diminishes. In comparison to the ruthenium series, the osmium analogues exhibit larger transition energies from enhanced MO splitting and a different EPR response due to the higher spin–orbit coupling. The main difference between the quinone (1n, 2n) and corresponding monoiminoquinone systems (3n, 4n) is the shift of about 0.6 V to lower potentials for the monoimino analogues. While the absorption features do not differ markedly, the EPR data reflect a higher degree of covalent bonding for the complexes with monoimino ligands. (en)
Title	UV-vis-NIR and EPR characterisation of the redox series [MQ3]2+,+,0,,2, M = Ru or Os, and Q = o-quinone derivative UV-vis-NIR and EPR characterisation of the redox series [MQ3]2+,+,0,,2, M = Ru or Os, and Q = o-quinone derivative (en)
skos:prefLabel	UV-vis-NIR and EPR characterisation of the redox series [MQ3]2+,+,0,,2, M = Ru or Os, and Q = o-quinone derivative UV-vis-NIR and EPR characterisation of the redox series [MQ3]2+,+,0,,2, M = Ru or Os, and Q = o-quinone derivative (en)
skos:notation	RIV/61388955:_____/12:00379014!RIV13-AV0-61388955
http://linked.open...avai/predkladatel	Ústav fyzikální chemie J. Heyrovského AV ČR, v.v.i.
http://linked.open...avai/riv/aktivita	I P
http://linked.open...avai/riv/aktivity	I, P(LD11086)
http://linked.open...iv/cisloPeriodika	29
http://linked.open...vai/riv/dodaniDat	2013
http://linked.open...aciTvurceVysledku	Fiedler, Jan Záliš, Stanislav
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Ústav fyzikální chemie J. Heyrovského AV ČR, v.v.i.
http://linked.open...dnocenehoVysledku	176767
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/12:00379014
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	physical chemistry; EPR spectroscopy; UV-vis-NIR (en)
http://linked.open.../riv/klicoveSlovo	EPR spectroscopy physical chemistry UV-vis-NIR
http://linked.open...odStatuVydavatele	GB - Spojené království Velké Británie a Severního Irska
http://linked.open...ontrolniKodProRIV	[5844A26BD67D]
http://linked.open...i/riv/nazevZdroje	Dalton Transactions
http://linked.open...in/vavai/riv/obor	CF
http://linked.open...ichTvurcuVysledku	2 (xsd:int)
http://linked.open...cetTvurcuVysledku	7 (xsd:int)
http://linked.open...vavai/riv/projekt	Quantum chemical interpretation and prediction of spectral characteristics of heavy transition metal complexes
http://linked.open...UplatneniVysledku	2012
http://linked.open...v/svazekPeriodika	41
http://linked.open...iv/tvurceVysledku	Fiedler, Jan Kaim, W. Lahiri, G. K. Sarkar, B. Záliš, Stanislav Hübner, R. Das, A. K.
http://linked.open...ain/vavai/riv/wos	000305891100021
issn	1477-9226
number of pages	9 (xsd:int)
http://bibframe.org/vocab/doi	10.1039/C2DT30846K
is http://linked.open...avai/riv/vysledek of	UV-vis-NIR and EPR characterisation of the redox series [MQ3]2+,+,0,,2, M = Ru or Os, and Q = o-quinone derivative

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