(NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system

Roger D. Willett, Carlos J. Gómez-García, B. L. Ramakrishna, Brendan Twamley

    Research output: Research - peer-reviewArticle

    • 32 Citations

    Abstract

    The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2- dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt) 2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order-disorder type involving one arm of the NBu4+ cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) Å and β = 115.642(3)° with V = 6020.8(11) Å3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) Å and β = 115.073(2)° and V = 5652.1(9) Å3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction. In the high temperature phase, the Ni-S distances between anions are accidentally equal, and the stacks behave as nearly uniform antiferromagnetic chains with nearly equal exchange constants. At the phase transition, a non-uniform compression of the stacks occurs and the magnetic moment drops rapidly, indicating a magnetic dimerization of the stacks. Susceptibility and Cp measurements show an approximate 7°C thermal hysteresis.

    LanguageEnglish (US)
    Pages2232-2237
    Number of pages6
    JournalPolyhedron
    Volume24
    Issue number16-17
    DOIs
    StatePublished - Nov 17 2005

    Fingerprint

    Phase transitions
    Temperature
    Phase Transition
    Anions
    Negative ions
    anions
    Order disorder transitions
    Dimerization
    Nickel
    Magnetic moments
    Hysteresis
    Cations
    Cooling
    Hot Temperature
    Direction compound
    tetrabutylammonium
    Positive ions
    dimerization
    magnetic moments
    hysteresis

    Keywords

    • Antiferromagnetic chain
    • Bistable behavior
    • Crystal structure
    • Dimerization
    • Nickel dithiolate complex
    • Phase transition

    ASJC Scopus subject areas

    • Biochemistry
    • Inorganic Chemistry
    • Physical and Theoretical Chemistry
    • Materials Chemistry

    Cite this

    Willett, R. D., Gómez-García, C. J., Ramakrishna, B. L., & Twamley, B. (2005). (NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system. Polyhedron, 24(16-17), 2232-2237. DOI: 10.1016/j.poly.2005.03.088

    (NBu4)Ni(mnt)2 : A novel bistable high temperature spin-Peierls-like system. / Willett, Roger D.; Gómez-García, Carlos J.; Ramakrishna, B. L.; Twamley, Brendan.

    In: Polyhedron, Vol. 24, No. 16-17, 17.11.2005, p. 2232-2237.

    Research output: Research - peer-reviewArticle

    Willett, RD, Gómez-García, CJ, Ramakrishna, BL & Twamley, B 2005, '(NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system' Polyhedron, vol 24, no. 16-17, pp. 2232-2237. DOI: 10.1016/j.poly.2005.03.088
    Willett RD, Gómez-García CJ, Ramakrishna BL, Twamley B. (NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system. Polyhedron. 2005 Nov 17;24(16-17):2232-2237. Available from, DOI: 10.1016/j.poly.2005.03.088
    Willett, Roger D. ; Gómez-García, Carlos J. ; Ramakrishna, B. L. ; Twamley, Brendan. / (NBu4)Ni(mnt)2 : A novel bistable high temperature spin-Peierls-like system. In: Polyhedron. 2005 ; Vol. 24, No. 16-17. pp. 2232-2237
    @article{ed761fd97b974d679b71d14357740231,
    title = "(NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system",
    abstract = "The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2- dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt) 2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order-disorder type involving one arm of the NBu4+ cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) Å and β = 115.642(3)° with V = 6020.8(11) Å3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) Å and β = 115.073(2)° and V = 5652.1(9) Å3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction. In the high temperature phase, the Ni-S distances between anions are accidentally equal, and the stacks behave as nearly uniform antiferromagnetic chains with nearly equal exchange constants. At the phase transition, a non-uniform compression of the stacks occurs and the magnetic moment drops rapidly, indicating a magnetic dimerization of the stacks. Susceptibility and Cp measurements show an approximate 7°C thermal hysteresis.",
    keywords = "Antiferromagnetic chain, Bistable behavior, Crystal structure, Dimerization, Nickel dithiolate complex, Phase transition",
    author = "Willett, {Roger D.} and Gómez-García, {Carlos J.} and Ramakrishna, {B. L.} and Brendan Twamley",
    year = "2005",
    month = "11",
    doi = "10.1016/j.poly.2005.03.088",
    volume = "24",
    pages = "2232--2237",
    journal = "Polyhedron",
    issn = "0277-5387",
    publisher = "Elsevier Limited",
    number = "16-17",

    }

    TY - JOUR

    T1 - (NBu4)Ni(mnt)2

    T2 - Polyhedron

    AU - Willett,Roger D.

    AU - Gómez-García,Carlos J.

    AU - Ramakrishna,B. L.

    AU - Twamley,Brendan

    PY - 2005/11/17

    Y1 - 2005/11/17

    N2 - The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2- dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt) 2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order-disorder type involving one arm of the NBu4+ cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) Å and β = 115.642(3)° with V = 6020.8(11) Å3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) Å and β = 115.073(2)° and V = 5652.1(9) Å3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction. In the high temperature phase, the Ni-S distances between anions are accidentally equal, and the stacks behave as nearly uniform antiferromagnetic chains with nearly equal exchange constants. At the phase transition, a non-uniform compression of the stacks occurs and the magnetic moment drops rapidly, indicating a magnetic dimerization of the stacks. Susceptibility and Cp measurements show an approximate 7°C thermal hysteresis.

    AB - The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2- dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt) 2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order-disorder type involving one arm of the NBu4+ cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) Å and β = 115.642(3)° with V = 6020.8(11) Å3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) Å and β = 115.073(2)° and V = 5652.1(9) Å3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction. In the high temperature phase, the Ni-S distances between anions are accidentally equal, and the stacks behave as nearly uniform antiferromagnetic chains with nearly equal exchange constants. At the phase transition, a non-uniform compression of the stacks occurs and the magnetic moment drops rapidly, indicating a magnetic dimerization of the stacks. Susceptibility and Cp measurements show an approximate 7°C thermal hysteresis.

    KW - Antiferromagnetic chain

    KW - Bistable behavior

    KW - Crystal structure

    KW - Dimerization

    KW - Nickel dithiolate complex

    KW - Phase transition

    UR - http://www.scopus.com/inward/record.url?scp=27744584908&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=27744584908&partnerID=8YFLogxK

    U2 - 10.1016/j.poly.2005.03.088

    DO - 10.1016/j.poly.2005.03.088

    M3 - Article

    VL - 24

    SP - 2232

    EP - 2237

    JO - Polyhedron

    JF - Polyhedron

    SN - 0277-5387

    IS - 16-17

    ER -