Formation of isomorphic Ir3+ and Ir4+ octamers and spin dimerization in the spinel CuIr2S4

Paolo G. Radaelli, Y. Horibe, Matthias J. Gutmann, Hiroki Ishibashi, C. H. Chen, Richard M. Ibberson, Yasumasa Koyama, Yew San Hor, Valery Kiryukhin, Sang Wook Cheong

    Research output: Contribution to journalArticle

    237 Citations (Scopus)

    Abstract

    Inorganic compounds with the AB2X4 spinel structure have been studied for many years, because of their unusual physical properties. The spinel crystallographic structure, first solved by Bragg in 1915, has cations occupying both tetrahedral (A) and octahedral (B) sites. Interesting physics arises when the B-site cations become mixed in valence. Magnetite (Fe3O4) is a classic and still unresolved example, where the tendency to form ordered arrays of Fe2+ and Fe3+ ions competes with the topological frustration of the B-site network. The CuIr2S4 thiospinel is another example, well known for the presence of a metal-insulator transition at 230 K with an abrupt decrease of the electrical conductivity on cooling accompanied by the loss of localized magnetic moments. Here, we report the determination of the crystallographic structure of CuIr2S4 below the metal-insulator transition. Our results indicate that CuIr2S4 undergoes a simultaneous charge-ordering and spin-dimerization transition - a rare phenomenon in three-dimensional compounds. Remarkably, the charge-ordering pattern consists of isomorphic octamers of Ir8 3+S24 and Ir8 4+S24 (as isovalent bi-capped hexagonal rings). This extraordinary arrangement leads to an elegant description of the spinel structure, but represents an increase in complexity with respect to all the known charge-ordered structures, which are typically based on stripes, slabs or chequerboard patterns.

    Original languageEnglish
    Pages (from-to)155-158
    Number of pages4
    JournalNature
    Volume416
    Issue number6877
    DOIs
    Publication statusPublished - 2002 Mar 14

    Fingerprint

    Dimerization
    Cations
    Metals
    Ferrosoferric Oxide
    Electric Conductivity
    Frustration
    Physics
    Ions
    spinell

    ASJC Scopus subject areas

    • General

    Cite this

    Radaelli, P. G., Horibe, Y., Gutmann, M. J., Ishibashi, H., Chen, C. H., Ibberson, R. M., ... Cheong, S. W. (2002). Formation of isomorphic Ir3+ and Ir4+ octamers and spin dimerization in the spinel CuIr2S4 Nature, 416(6877), 155-158. https://doi.org/10.1038/416155a

    Formation of isomorphic Ir3+ and Ir4+ octamers and spin dimerization in the spinel CuIr2S4 . / Radaelli, Paolo G.; Horibe, Y.; Gutmann, Matthias J.; Ishibashi, Hiroki; Chen, C. H.; Ibberson, Richard M.; Koyama, Yasumasa; Hor, Yew San; Kiryukhin, Valery; Cheong, Sang Wook.

    In: Nature, Vol. 416, No. 6877, 14.03.2002, p. 155-158.

    Research output: Contribution to journalArticle

    Radaelli, PG, Horibe, Y, Gutmann, MJ, Ishibashi, H, Chen, CH, Ibberson, RM, Koyama, Y, Hor, YS, Kiryukhin, V & Cheong, SW 2002, 'Formation of isomorphic Ir3+ and Ir4+ octamers and spin dimerization in the spinel CuIr2S4 ', Nature, vol. 416, no. 6877, pp. 155-158. https://doi.org/10.1038/416155a
    Radaelli PG, Horibe Y, Gutmann MJ, Ishibashi H, Chen CH, Ibberson RM et al. Formation of isomorphic Ir3+ and Ir4+ octamers and spin dimerization in the spinel CuIr2S4 Nature. 2002 Mar 14;416(6877):155-158. https://doi.org/10.1038/416155a
    Radaelli, Paolo G. ; Horibe, Y. ; Gutmann, Matthias J. ; Ishibashi, Hiroki ; Chen, C. H. ; Ibberson, Richard M. ; Koyama, Yasumasa ; Hor, Yew San ; Kiryukhin, Valery ; Cheong, Sang Wook. / Formation of isomorphic Ir3+ and Ir4+ octamers and spin dimerization in the spinel CuIr2S4 In: Nature. 2002 ; Vol. 416, No. 6877. pp. 155-158.
    @article{4b3be4e30a25451983148f67a7c2966b,
    title = "Formation of isomorphic Ir3+ and Ir4+ octamers and spin dimerization in the spinel CuIr2S4",
    abstract = "Inorganic compounds with the AB2X4 spinel structure have been studied for many years, because of their unusual physical properties. The spinel crystallographic structure, first solved by Bragg in 1915, has cations occupying both tetrahedral (A) and octahedral (B) sites. Interesting physics arises when the B-site cations become mixed in valence. Magnetite (Fe3O4) is a classic and still unresolved example, where the tendency to form ordered arrays of Fe2+ and Fe3+ ions competes with the topological frustration of the B-site network. The CuIr2S4 thiospinel is another example, well known for the presence of a metal-insulator transition at 230 K with an abrupt decrease of the electrical conductivity on cooling accompanied by the loss of localized magnetic moments. Here, we report the determination of the crystallographic structure of CuIr2S4 below the metal-insulator transition. Our results indicate that CuIr2S4 undergoes a simultaneous charge-ordering and spin-dimerization transition - a rare phenomenon in three-dimensional compounds. Remarkably, the charge-ordering pattern consists of isomorphic octamers of Ir8 3+S24 and Ir8 4+S24 (as isovalent bi-capped hexagonal rings). This extraordinary arrangement leads to an elegant description of the spinel structure, but represents an increase in complexity with respect to all the known charge-ordered structures, which are typically based on stripes, slabs or chequerboard patterns.",
    author = "Radaelli, {Paolo G.} and Y. Horibe and Gutmann, {Matthias J.} and Hiroki Ishibashi and Chen, {C. H.} and Ibberson, {Richard M.} and Yasumasa Koyama and Hor, {Yew San} and Valery Kiryukhin and Cheong, {Sang Wook}",
    year = "2002",
    month = "3",
    day = "14",
    doi = "10.1038/416155a",
    language = "English",
    volume = "416",
    pages = "155--158",
    journal = "Nature",
    issn = "0028-0836",
    publisher = "Nature Publishing Group",
    number = "6877",

    }

    TY - JOUR

    T1 - Formation of isomorphic Ir3+ and Ir4+ octamers and spin dimerization in the spinel CuIr2S4

    AU - Radaelli, Paolo G.

    AU - Horibe, Y.

    AU - Gutmann, Matthias J.

    AU - Ishibashi, Hiroki

    AU - Chen, C. H.

    AU - Ibberson, Richard M.

    AU - Koyama, Yasumasa

    AU - Hor, Yew San

    AU - Kiryukhin, Valery

    AU - Cheong, Sang Wook

    PY - 2002/3/14

    Y1 - 2002/3/14

    N2 - Inorganic compounds with the AB2X4 spinel structure have been studied for many years, because of their unusual physical properties. The spinel crystallographic structure, first solved by Bragg in 1915, has cations occupying both tetrahedral (A) and octahedral (B) sites. Interesting physics arises when the B-site cations become mixed in valence. Magnetite (Fe3O4) is a classic and still unresolved example, where the tendency to form ordered arrays of Fe2+ and Fe3+ ions competes with the topological frustration of the B-site network. The CuIr2S4 thiospinel is another example, well known for the presence of a metal-insulator transition at 230 K with an abrupt decrease of the electrical conductivity on cooling accompanied by the loss of localized magnetic moments. Here, we report the determination of the crystallographic structure of CuIr2S4 below the metal-insulator transition. Our results indicate that CuIr2S4 undergoes a simultaneous charge-ordering and spin-dimerization transition - a rare phenomenon in three-dimensional compounds. Remarkably, the charge-ordering pattern consists of isomorphic octamers of Ir8 3+S24 and Ir8 4+S24 (as isovalent bi-capped hexagonal rings). This extraordinary arrangement leads to an elegant description of the spinel structure, but represents an increase in complexity with respect to all the known charge-ordered structures, which are typically based on stripes, slabs or chequerboard patterns.

    AB - Inorganic compounds with the AB2X4 spinel structure have been studied for many years, because of their unusual physical properties. The spinel crystallographic structure, first solved by Bragg in 1915, has cations occupying both tetrahedral (A) and octahedral (B) sites. Interesting physics arises when the B-site cations become mixed in valence. Magnetite (Fe3O4) is a classic and still unresolved example, where the tendency to form ordered arrays of Fe2+ and Fe3+ ions competes with the topological frustration of the B-site network. The CuIr2S4 thiospinel is another example, well known for the presence of a metal-insulator transition at 230 K with an abrupt decrease of the electrical conductivity on cooling accompanied by the loss of localized magnetic moments. Here, we report the determination of the crystallographic structure of CuIr2S4 below the metal-insulator transition. Our results indicate that CuIr2S4 undergoes a simultaneous charge-ordering and spin-dimerization transition - a rare phenomenon in three-dimensional compounds. Remarkably, the charge-ordering pattern consists of isomorphic octamers of Ir8 3+S24 and Ir8 4+S24 (as isovalent bi-capped hexagonal rings). This extraordinary arrangement leads to an elegant description of the spinel structure, but represents an increase in complexity with respect to all the known charge-ordered structures, which are typically based on stripes, slabs or chequerboard patterns.

    UR - http://www.scopus.com/inward/record.url?scp=18344381412&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=18344381412&partnerID=8YFLogxK

    U2 - 10.1038/416155a

    DO - 10.1038/416155a

    M3 - Article

    VL - 416

    SP - 155

    EP - 158

    JO - Nature

    JF - Nature

    SN - 0028-0836

    IS - 6877

    ER -