Intramolecular dynamics of asymmetric lanthanide(III) porphyrin sandwich complexes in solution

Sergey P. Babailov, Athanassios G. Coutsolelos, Alexander Dikiy, Georgios A. Spyroulias

    Research output: Contribution to journalArticle

    32 Citations (Scopus)

    Abstract

    Temperature dependencies of the 1H NMR spectra of asymmetric double-decker complexes of DyH(oep)(tpp) (I) and LuH(oep)(tpp) (II), where tpp is tetraphenylporphyrin and oep is octaethylporphyrin, have been analyzed. The kinetic and thermodynamic parameters for intramolecular phenyl ring rotations have been determined. The rotation in (I) is characterized by k(298 K) = 11.4 s-1, ΔH = 48.0±6.0 kJ mol-1, while in (II) the derived parameters are found to be k(298 K) = 14.0 s-1, ΔH = 65.5±7.1 kJ mol-1. The possible reasons for the different characteristics of these complexes are discussed. The structural parameters calculated for I and YbH(oep)(tpp) (III), indicate close similarities between the complexes. Nevertheless, it appears that the principal values of the molar paramagnetic susceptibility tensor (χi) differ significantly in these complexes.

    Original languageEnglish
    Pages (from-to)303-306
    Number of pages4
    JournalEuropean Journal of Inorganic Chemistry
    Issue number1
    DOIs
    Publication statusPublished - 2001

    Fingerprint

    Lanthanoid Series Elements
    Porphyrins
    Tensors
    Nuclear magnetic resonance
    Thermodynamics
    Kinetics
    Temperature
    tetraphenylporphyrin
    octaethylporphyrin

    Keywords

    • Lanthanides
    • Metalloporphyrins
    • NMR spectroscopy
    • Phenyl ring rotation

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Intramolecular dynamics of asymmetric lanthanide(III) porphyrin sandwich complexes in solution. / Babailov, Sergey P.; Coutsolelos, Athanassios G.; Dikiy, Alexander; Spyroulias, Georgios A.

    In: European Journal of Inorganic Chemistry, No. 1, 2001, p. 303-306.

    Research output: Contribution to journalArticle

    Babailov, Sergey P. ; Coutsolelos, Athanassios G. ; Dikiy, Alexander ; Spyroulias, Georgios A. / Intramolecular dynamics of asymmetric lanthanide(III) porphyrin sandwich complexes in solution. In: European Journal of Inorganic Chemistry. 2001 ; No. 1. pp. 303-306.
    @article{8acd4b6f018b4213b3e9ba148af92173,
    title = "Intramolecular dynamics of asymmetric lanthanide(III) porphyrin sandwich complexes in solution",
    abstract = "Temperature dependencies of the 1H NMR spectra of asymmetric double-decker complexes of DyH(oep)(tpp) (I) and LuH(oep)(tpp) (II), where tpp is tetraphenylporphyrin and oep is octaethylporphyrin, have been analyzed. The kinetic and thermodynamic parameters for intramolecular phenyl ring rotations have been determined. The rotation in (I) is characterized by k(298 K) = 11.4 s-1, ΔH‡ = 48.0±6.0 kJ mol-1, while in (II) the derived parameters are found to be k(298 K) = 14.0 s-1, ΔH‡ = 65.5±7.1 kJ mol-1. The possible reasons for the different characteristics of these complexes are discussed. The structural parameters calculated for I and YbH(oep)(tpp) (III), indicate close similarities between the complexes. Nevertheless, it appears that the principal values of the molar paramagnetic susceptibility tensor (χi) differ significantly in these complexes.",
    keywords = "Lanthanides, Metalloporphyrins, NMR spectroscopy, Phenyl ring rotation",
    author = "Babailov, {Sergey P.} and Coutsolelos, {Athanassios G.} and Alexander Dikiy and Spyroulias, {Georgios A.}",
    year = "2001",
    doi = "10.1002/1099-0682(20011)2001:1<303::AID-EJIC303>3.0.CO;2-Y",
    language = "English",
    pages = "303--306",
    journal = "Chemische Berichte",
    issn = "0009-2940",
    publisher = "Wiley-VCH Verlag",
    number = "1",

    }

    TY - JOUR

    T1 - Intramolecular dynamics of asymmetric lanthanide(III) porphyrin sandwich complexes in solution

    AU - Babailov, Sergey P.

    AU - Coutsolelos, Athanassios G.

    AU - Dikiy, Alexander

    AU - Spyroulias, Georgios A.

    PY - 2001

    Y1 - 2001

    N2 - Temperature dependencies of the 1H NMR spectra of asymmetric double-decker complexes of DyH(oep)(tpp) (I) and LuH(oep)(tpp) (II), where tpp is tetraphenylporphyrin and oep is octaethylporphyrin, have been analyzed. The kinetic and thermodynamic parameters for intramolecular phenyl ring rotations have been determined. The rotation in (I) is characterized by k(298 K) = 11.4 s-1, ΔH‡ = 48.0±6.0 kJ mol-1, while in (II) the derived parameters are found to be k(298 K) = 14.0 s-1, ΔH‡ = 65.5±7.1 kJ mol-1. The possible reasons for the different characteristics of these complexes are discussed. The structural parameters calculated for I and YbH(oep)(tpp) (III), indicate close similarities between the complexes. Nevertheless, it appears that the principal values of the molar paramagnetic susceptibility tensor (χi) differ significantly in these complexes.

    AB - Temperature dependencies of the 1H NMR spectra of asymmetric double-decker complexes of DyH(oep)(tpp) (I) and LuH(oep)(tpp) (II), where tpp is tetraphenylporphyrin and oep is octaethylporphyrin, have been analyzed. The kinetic and thermodynamic parameters for intramolecular phenyl ring rotations have been determined. The rotation in (I) is characterized by k(298 K) = 11.4 s-1, ΔH‡ = 48.0±6.0 kJ mol-1, while in (II) the derived parameters are found to be k(298 K) = 14.0 s-1, ΔH‡ = 65.5±7.1 kJ mol-1. The possible reasons for the different characteristics of these complexes are discussed. The structural parameters calculated for I and YbH(oep)(tpp) (III), indicate close similarities between the complexes. Nevertheless, it appears that the principal values of the molar paramagnetic susceptibility tensor (χi) differ significantly in these complexes.

    KW - Lanthanides

    KW - Metalloporphyrins

    KW - NMR spectroscopy

    KW - Phenyl ring rotation

    UR - http://www.scopus.com/inward/record.url?scp=0035188464&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=0035188464&partnerID=8YFLogxK

    U2 - 10.1002/1099-0682(20011)2001:1<303::AID-EJIC303>3.0.CO;2-Y

    DO - 10.1002/1099-0682(20011)2001:1<303::AID-EJIC303>3.0.CO;2-Y

    M3 - Article

    SP - 303

    EP - 306

    JO - Chemische Berichte

    JF - Chemische Berichte

    SN - 0009-2940

    IS - 1

    ER -