Optically Detected ESR and Low Magnetic Field Signals from Spin Triads

2-Imidazoline-1-Oxyl Derivatives in X-Irradiated Alkane Liquids as a Method to Study Three-Spin Systems

Fyodor B. Sviridenko, Dmitri V. Stass, Tatyana V. Kobzeva, Evgeny V. Tretyakov, Svetlana V. Klyatskaya, Elena V. Mshvidobadze, Sergey F. Vasilevsky, Yuri N. Molin

    Research output: Contribution to journalArticle

    42 Citations (Scopus)

    Abstract

    This contribution reports the design and synthesis of a series of spin-labeled charge acceptors to produce three-spin systems of "radical ion/biradical ion" type in X-irradiated alkane liquids. This opens the way to study spin triads in experimental conditions, in which short-lived radical ion pairs are conventionally studied, thus offering optically detected techniques such as magneto-resonance OD ESR and level-crossing MARY spectroscopy. The structure of the synthesized 2-imidazoline-1-oxyl derivatives is A-Sp-R, where A is a positive or negative charge acceptor, R is a stable radical, and Sp is a hydrocarbon bridge. The set of 20+ compounds represent a convenient tool to construct experimental three-spin systems with various properties, e.g. with the "third" spin introduced into one or the other partner of the radical ion pair. The degree of exchange coupling between the two paramagnetic fragments in the biradical ion has been demonstrated to strongly depend on the type of the radical fragment R and the structure of the bridge Sp. As a result, a series of acceptors with systematically reduced exchange interaction has been synthesized, and optimal systems for the observation of low magnetic field effect have been found. In the most favorable case, an OD ESR signal from a spin triad living as short as ca. 100 ns has been registered as a single unresolved line. The exchange integral for this biradical anion (9) was estimated from OD ESR and ESR experiments to be ca. 103 G by the order of magnitude, which is much greater than the hyperfine couplings in the biradical ion but much smaller than the thermal energy kT.

    Original languageEnglish
    Pages (from-to)2807-2819
    Number of pages13
    JournalJournal of the American Chemical Society
    Volume126
    Issue number9
    DOIs
    Publication statusPublished - 10 Mar 2004

    Fingerprint

    Alkanes
    Magnetic Fields
    Paraffins
    Paramagnetic resonance
    Ions
    Magnetic fields
    Derivatives
    Liquids
    Magnetic field effects
    Optimal systems
    Exchange coupling
    Exchange interactions
    Hydrocarbons
    Thermal energy
    Anions
    2-imidazoline
    Spectrum Analysis
    Ion exchange
    Negative ions
    Hot Temperature

    ASJC Scopus subject areas

    • Catalysis
    • Chemistry(all)
    • Biochemistry
    • Colloid and Surface Chemistry

    Cite this

    Optically Detected ESR and Low Magnetic Field Signals from Spin Triads : 2-Imidazoline-1-Oxyl Derivatives in X-Irradiated Alkane Liquids as a Method to Study Three-Spin Systems. / Sviridenko, Fyodor B.; Stass, Dmitri V.; Kobzeva, Tatyana V.; Tretyakov, Evgeny V.; Klyatskaya, Svetlana V.; Mshvidobadze, Elena V.; Vasilevsky, Sergey F.; Molin, Yuri N.

    In: Journal of the American Chemical Society, Vol. 126, No. 9, 10.03.2004, p. 2807-2819.

    Research output: Contribution to journalArticle

    Sviridenko, Fyodor B. ; Stass, Dmitri V. ; Kobzeva, Tatyana V. ; Tretyakov, Evgeny V. ; Klyatskaya, Svetlana V. ; Mshvidobadze, Elena V. ; Vasilevsky, Sergey F. ; Molin, Yuri N. / Optically Detected ESR and Low Magnetic Field Signals from Spin Triads : 2-Imidazoline-1-Oxyl Derivatives in X-Irradiated Alkane Liquids as a Method to Study Three-Spin Systems. In: Journal of the American Chemical Society. 2004 ; Vol. 126, No. 9. pp. 2807-2819.
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    abstract = "This contribution reports the design and synthesis of a series of spin-labeled charge acceptors to produce three-spin systems of {"}radical ion/biradical ion{"} type in X-irradiated alkane liquids. This opens the way to study spin triads in experimental conditions, in which short-lived radical ion pairs are conventionally studied, thus offering optically detected techniques such as magneto-resonance OD ESR and level-crossing MARY spectroscopy. The structure of the synthesized 2-imidazoline-1-oxyl derivatives is A-Sp-R, where A is a positive or negative charge acceptor, R is a stable radical, and Sp is a hydrocarbon bridge. The set of 20+ compounds represent a convenient tool to construct experimental three-spin systems with various properties, e.g. with the {"}third{"} spin introduced into one or the other partner of the radical ion pair. The degree of exchange coupling between the two paramagnetic fragments in the biradical ion has been demonstrated to strongly depend on the type of the radical fragment R and the structure of the bridge Sp. As a result, a series of acceptors with systematically reduced exchange interaction has been synthesized, and optimal systems for the observation of low magnetic field effect have been found. In the most favorable case, an OD ESR signal from a spin triad living as short as ca. 100 ns has been registered as a single unresolved line. The exchange integral for this biradical anion (9) was estimated from OD ESR and ESR experiments to be ca. 103 G by the order of magnitude, which is much greater than the hyperfine couplings in the biradical ion but much smaller than the thermal energy kT.",
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    AU - Sviridenko, Fyodor B.

    AU - Stass, Dmitri V.

    AU - Kobzeva, Tatyana V.

    AU - Tretyakov, Evgeny V.

    AU - Klyatskaya, Svetlana V.

    AU - Mshvidobadze, Elena V.

    AU - Vasilevsky, Sergey F.

    AU - Molin, Yuri N.

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