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Intramolecular Valence and Spin Interaction in meso and rac Diastereomers of a p-Quinonoid-Bridged Diruthenium Complex

The result's identifiers

  • Result code in IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F08%3A00321038" target="_blank" >RIV/61388955:_____/08:00321038 - isvavai.cz</a>

  • Result on the web

  • DOI - Digital Object Identifier

Alternative languages

  • Result language

    angličtina

  • Original language name

    Intramolecular Valence and Spin Interaction in meso and rac Diastereomers of a p-Quinonoid-Bridged Diruthenium Complex

  • Original language description

    The complexes rac- and meso-[(acac)2Ru(.mu.-L)Ru(acac)2]n , 1 and 2, where L2- = 1,4-dioxido-2,3-bis(3,5-dimethylpyrazol-1´-yl)benzene and acac- = 2,4-pentanedionato, were characterized structurally, magnetically, electrochemically and spectroscopicallyas well as spectroelectrochemically (UV-Vis-NIR, EPR) in the accessible redox states (n = 0,+,-,2-). Susceptibility and EPR measurements confirm the {RuIII(.mu.-L2´´)RuIII} configuration of the neutral species. Two-step reduction involves the metals andproduces RuIIIRuII mixed-valent monoanions with broad intervalence charge transfer (IVCT) bands, suggesting localized valence (class II). Oxidation produces intense near-infrared (NIR) absorption and narrow isotropic EPR spectra at g = 2.005, signifyingunprecedented spin localization at the p-semiquinone bridge. These results are compatible with the {RuIII(.mu.-L.-)RuIII} situation with up-up-down spin configuration, strong antiferromagnetic coupling between the remote metal spins.

  • Czech name

    Intramolekulární valenční a spinová interakce v rac a meso diastereomerech diirutheniového komplexu s p-chinonoidním můstkem

  • Czech description

    Komplexy rac- a meso-[(acac)2Ru(.mu.-L)Ru(acac)2]n , 1 a 2, kde L2- = 1,4-dioxido-2,3-bis(3,5-dimethylpyrazol-1´-yl)benzen a acac- = 2,4-pentanedionato, byl charakterizován strukturálně, magneticky, elektrochemicky, spektrálně a spektroelektrochemicky (UV-VIS-NIR, EPR ) v dostupných redox stavech (n = 0,+, -,2-). Susceptibilita a EPR měření potvrdila {RuIII(.mu.-L2´´) RuIII} konfiguraci neutrální molekuly. Dvoustupňová redukce zahrnuje kovy a produkuje monoanionty se smíšenou valencí RuIIIRuII, s širokými intervalenčními pásy přenosu náboje (IVCT), naznačující lokalizovanou valenci (třída II). Oxidace dává intenzivní absorbci v blízké infračervené oblasti (NIR ) a úzká isotropická EPR spektra s g = 2.005, jež ukazují na nezvyklou lokalizaci spinu na p-semichinonovém můstku. Tyto výsledky jsou kompatibilní s {RuIII(.mu.-L2.-) RuIII} situací se spinovou konfigurací nahoru-nahoru-dolů, silnou antiferromagnetickou interakcí mezi vzdáleným spiny kovů.

Classification

  • Type

    J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

  • CEP classification

    CF - Physical chemistry and theoretical chemistry

  • OECD FORD branch

Result continuities

  • Project

    Result was created during the realization of more than one project. More information in the Projects tab.

  • Continuities

    Z - Vyzkumny zamer (s odkazem do CEZ)

Others

  • Publication year

    2008

  • Confidentiality

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Data specific for result type

  • Name of the periodical

    Journal of the American Chemical Society

  • ISSN

    0002-7863

  • e-ISSN

  • Volume of the periodical

    130

  • Issue of the periodical within the volume

    51

  • Country of publishing house

    US - UNITED STATES

  • Number of pages

    9

  • Pages from-to

  • UT code for WoS article

    000263320600074

  • EID of the result in the Scopus database